The agreement, which industry sources say is worth around £700,000, is the first major sports sponsorship by a government department.
It will see the forthcoming Rugby League Tests against the touring New Zealand team renamed the Think! Don't Drink Drive Test Series.
The deal is designed to boost awareness of the government's anti drink-drive campaign among 18- to 35-year-old men. However, it could arouse controversy on two counts: first for the difficulty of measuring the sponsorship's effectiveness, and second because alcohol brands including Tetley Bitter are also sponsors of rugby league properties.
A Rugby Football League (RFL) spokesman denied there was any conflict and said the sponsorship had the backing of its alcohol partners.
RFL executive chairman Richard Lewis said: "Rugby League has always prided itself on its social responsibility and this partnership is a tremendous way of both illustrating this and promoting the anti drink-drive message."
The deal will see the Think! branding appearing on the front of the team's shirts during their matches against the Kiwis.
An anti drink-drive policy is also being included in the contracts of players, managers, coaches and staff of all RFL representative teams.