The brand, the UK's leading nicotine replacement therapy (NRT) product, believes a move into the world of F1 will promote it around the world and that the sport's audience includes millions of smokers who are trying to kick the habit.
NiQuitin CQ's arrival on the Williams cars at this weekend's San Marino Grand Prix will be the first time an NRT brand has sponsored an F1 team.
During the 90s, the Rothmans cigarette brand was title sponsor of the Williams team.
Neither party would comment on the value of the deal, but industry sources suggested it could have cost GSK as much as £10m. Other sponsors of the Williams team include Hewlett-Packard, Castrol, Western Union and Reuters.
"We want to make giving up smoking using NiQuitin CQ more aspirational and F1 provides a perfect means to that end," said Mark Dickinson, marketing manager for Ni-Quitin CQ. "This is a perfect opportunity to inspire millions of smokers who have been bombarded with pro-tobacco messages through F1 for decades."
Tobacco brands continue to play a major role in F1, with the McLaren team backed by West, Jordan sponsored by Benson & Hedges, Ferrari sponsored by Marlboro and BAR supported by the Lucky Strike brand. In total, it is estimated that tobacco firms still pay more than £160m a year to associate their products with the sport.
The NiQuitin CQ deal with the BMW Williams team is one of the most significant F1 sponsorship agreements ever struck.
Finally, the pharmaceutical industry realises there is an opportunity to promote its smoking-cessation brands as tobacco's influence on the sport begins to wane.
The key to the deal's success will be the same as for any sponsor - can GSK create a marketing strategy that enables it to stand out in what remains a heavily-branded sporting circus?