The aim of the relationship is to target 17- to 19-year-olds, who make up only 1.5% of UK licence holders but are responsible for 12% of fatal and serious crashes.
Deyes, who passed his test following driving lessons provided by Direct Line, will be insured on its telematics policy for a year.
The policy allows the installation of a 'Drive Plus Plug In' device, which will monitor each journey. It records and suggests improvements on cornering, accelerating and speed. Deyes' adventures will be posted exclusively on Direct Line’s YouTube channel over the next four months and will link to his own PointlessBlogVlogs.
To kick off the campaign, Direct Line sent Deyes a Direct Fix red box of driving goodies which featured on his PointlessBlogVlogs channel, accumulating over 435,000 views.
Wendy Pearson, head of marketing at Direct Line, said: "We approached Alfie after discovering his 4.5m subscribers regularly joke about his lack of driving skills using the hashtag #alfiecantdrive.
"He is an excellent role model for young people who can inject a sense of fun into our campaign whilst assisting us in our ultimate goal of helping Britons to be better drivers."
To measure the success of the campaign, Direct Line will complete brand tracking and brand connotation for its site and will undertake soft social measurements such as views, likes, shares and follows.