Catalytic hydroalkylation reaction of alkenes with benzylic hydrocarbons involving t-BuOK/DMF-mediated benzylic C-H bond activation is demonstrated. This direct and operational simple protocol affords a rapid and reliable access to a wide scope of benzylic compounds in good-to-excellent yields. The benzylic C-H's of either activated diarylmethanes (pKa ∼ 32.2) and benzyl thioethers (pKa ∼ 30.8) or inert alkylbenzenes could all act as useful synthetic platforms to be conveniently alkylated under mild reaction conditions.