We report here on a C-H alkylation reaction, in which the coupling of aromatic ketones with alkenes proceeds in the presence of only a simple Fe(PMe3)(4) catalyst. The anti-Markovnikov addition of ortho C-H bonds in various ketones occurs with excellent regioselectivity under relatively mild reaction conditions. A strikingly wide variety of alkenes can be used for this reaction, and the high-yielding anti-Markovnikov addition of aromatic C-H bonds to enol ethers was achieved for the first time using this catalyst system.