1-Phenyl-2-vinyl-3,4-dimethylphosphole (4) was prepared from the corresponding 2-carboxaldehyde via a Wittig reaction. The reaction of its P-W(CO)5 complex 5 with [PhP-W(CO)5] selectively takes place at the vinyl double bond and gives the corresponding phosphirane 6 as a mixture of two diastereomers. The reaction of 4 with N-phenylmaleimide involves the phosphole dienic system and gives the [4 + 2] 7-phosphanorbornene cycloadduct 7. The reaction of 5 with dimethyl acetylenedicarboxylate either takes place at the phosphole dienic system and leads to the vinyl phthalate 10 with loss of the phosphorus bridge or involves the double bonds of the vinyl and one phosphole group to give the [4 + 2] cycloadduct 9, which is oxidized in situ to give 11 with two epoxides and one ketone functionality. The products 6, 7, 9, and 11 were characterized by X-ray crystal structure analysis. © 2014 American Chemical Society.