The drug, called varenicline, can help tackle smoking addiction by reducing the effects of nicotine on the brain, preventing cravings, and tackling withdrawal symptoms such as irritability, helping to stop people reaching for another cigarette.
The drug was previously licensed under the brand name Champix, but was withdrawn in 2021 after an impurity was discovered in the medicine.
The return of a new, improved version, manufactured by Teva UK, has been called a "game changer" by Amanda Pritchard, the NHS chief executive, who is expected to confirm a nationwide rollout during a speech at the NHS Providers' conference on Tuesday.
Officials estimate that more than 85,000 smokers could stand to benefit from the drug in each of the next five years, with 9,500 deaths caused by smoking being prevented.
It comes after the Tobacco and Vapes Bill was introduced in Parliament last week as the Government looks to create a "smokefree generation".
The pill could help one in four people stop smoking for at least six months when used alongside behavioural support, according to NHS England.
The drug is taken daily for 12 weeks under NHS guidance, and patients will be able to access it immediately through their GP or an NHS stop smoking service.
The cost of the 12-week treatment was previously about £164 for the branded version of the drug. The new cost has not been shared, but it is understood to be cheaper because the patent has expired and generic versions of the drug can now be widely produced.
Announcing the roll-out, Ms Pritchard will tell NHS leaders in Liverpool: "This simple, daily pill could be a game changer for people who want to quit smoking and is another vital step in shifting our NHS further towards prevention.
"Smoking remains one of the biggest public health issues facing the NHS and has devastating impacts on the body - from the lungs, to the heart, blood and brain, while also increasing risk of cancer, diabetes and stroke."
The relaunched version of varenicline has been approved by the safety regulator, the Medicines Health and Regulatory Authority (MHRA).
Another drug called cytisine, which tricks the brain into thinking someone has had a cigarette by attaching to the same receptors that nicotine does, is currently being reviewed by the National Institute for Health and Care Excellence.
Meanwhile, the return of the Tobacco and Vapes Bill, will seek to push through legislation to prevent anyone born from 2009 onwards from legally smoking, by gradually raising the age at which tobacco can be bought.
It also will introduce restrictions on vaping, as well as extending indoor smoking ban powers to some outdoor areas, including outside hospitals and in children's playgrounds, although it will stop short of a pub garden ban following a backlash.
Figures released last month by the Office for National Statistics suggest about 11.9 per cent of people aged 18 or over - the equivalent of about six million - smoked cigarettes in the UK last year.
The Government's 10-year plan for the NHS, which is expected to be published in spring, will also include a greater focus on sickness prevention.
As well as stricter rules on smoking and vaping, the Government is looking to tackle Britain's obesity epidemic and other preventable illnesses, including by introducing a junk food advertising ban.
"The roll-out of this pill can save the NHS millions of pounds, save appointments to help other patients be seen faster, and save lives.
"Taken alongside our Tobacco and Vapes Bill, the Government and NHS are building a healthy society to help power a healthy economy."
The NHS spends about £2.5 billion on treating health issues caused by smoking each year. It is the leading cause of preventable illness and deaths, causing more than seven in 10 lung cancers and increasing the risk of many major health conditions, such as strokes, diabetes, heart disease, stillbirth and dementia.
Previous analysis found that for every £1 spent on Champix with behavioural support, the NHS saved £1.65 on treating smoking-related illness or hospitalisations.
'Most effective'
Dr Sarah Jackson, a principal research fellow at the UCL Tobacco and Alcohol Research Group, said studies into varenicline had "consistently found it to be one of the most effective treatments for helping people to stop smoking".
Dr Ian Walker, executive director of policy at Cancer Research UK, added: "Along with funding for cessation services, making tools like this available will help more people stop smoking.
"Around 160 cases of cancer are caused by tobacco every day in the UK, so it's essential that action is taken to prevent people from smoking in the first place."
Henry Gregg, director of external affairs at Asthma + Lung UK, said: "While the Tobacco and Vapes Bill will protect younger generations from the harms caused by this deadly addiction, the hundreds of thousands of current smokers who want to give up must also be supported.
"It is incredibly difficult to quit smoking without help."