Alkyl aluminum compounds are widely applied in organic reactions because of their high reactivities, low toxicities, and ease of preparation. The cross-coupling reaction of an organoalane compounds with organic electrophiles using a transition-metal catalyst or catalyst-free provides a simple method to synthesize a large variety of compounds and shows a higher functional group tolerance than organolithium and magnesium, which allows for additions to aldehydes in the presence of nitro, ester, hydroxyl, amino, nitrile and lactone moieties. Therefore, many organoalane reagents have found the most applications in cross-coupling reactions in recent years. In this paper, the recent research results about the alkylaluminum reagents applied in cross-coupling reactions are reviewed, involving various reaction systems.