Shadow health secretary Andy Burnham is due to put an amendment of the Children's and Families Bill forward in the House of Lords on Wednesday that could ban drivers from smoking in cars with children inside.
Burnham told The Sunday Times: "Adults are free to make their own choices but that often does not apply to children and that's why society has an obligation to protect them from preventable harm.
"There is legislation banning the use of mobile phones when driving and requiring the wearing of seatbelts."
Scientific research has shown that smoking in a confined space, such as a car, increases toxic fume inhalation by passengers by up to 11 times compared to customers in a smoke-filled pub.
The move by Labour is in stark contrast to governments - both past and present - that have generally shied away from banning smoking in 'private places'.
According to The Daily Mail, a YouGov poll in 2011 found that 78% of adults agreed that smoking should be banned in cars carrying children under 18, while 44% said smoking should be banned in all cars.
If Labour succeeds with the amendment, it would make it an offence for motorists to smoke in a car that is transporting children under 18-years-old and offenders could face fines and points on the licence.
Civil liberty groups that still resent Labour for banning smoking in public places, such as pubs and restaurants, will likely fiercely oppose the ban.
If attempts to change the law fail, Labour will pledge to impose a ban if it wins next year's general election.