Six bisazidovinyl compounds (AVs) were synthesized for application to photosensitive materials. AVs easily yielded bifunctional 2H-azirine (AZ) in a thin polymer film of poly(1,2-butadiene (PB) or poly(4-hydroxystyrene) (POHSt) by heat treatment. By photoirradiation of those films, AZ yielded nitrile ylide (NY). The crosslinking reaction of the polymers proceeded through a 1,3-dipolar addition of NY with vinyl group (PB) and an addition with alcohol (POHSt). These reactions were confirmed by absorption and infrared spectra. The irradiated polymer films were insoluble in chloroform. The most sensitive AV compound is 2,7-bis(1-azidoethenyl)-dibenzothiophene, which can reproduce line-and-space patterns at 1.2 mJ cm⁻² (PB thin film with 254 nm photoirradiation).