In the current work, a palladium-catalyzed C-C bond cleavage reaction of primary alcohols has been developed. This transformation was characterized by a broad substrate scope, superior functional group tolerance, and high efficiency for selective C-C bond cleavage and was then followed by alkynyl-aryl cross coupling. Mechanism studies indicated that the propargyl alcohols underwent β-H elimination to form aldehydes rather than having undergone β-C elimination. The corresponding aldehyde intermediates then proceeded through a decarbonylation and coupling reaction with haloarenes to yield diarylacetylenes.