A silver-catalyzed phosphorylation/cyclization radical cascade of 1,6-dienes has been developed. The reaction process involves in a one-pot operation described as an autotandem catalytic process with a cascading radical cyclization for the construction of C—P and C—C bond with high stereoselectivity. Moreover, it also affords an efficient method for the synthesis of valuable exocyclic phosphine oxides compounds with broad substrate applicability, mild reaction condition and succinct reaction system.