Experiments concerning the photochemical condensation of 3-phenyl-2H-azirines 1 with aliphatic and aromatic aldehydes to 3-oxazolines 4 are fully described (cf. scheme 1). Photochemically nitrile methylides of type 2 are first formed, which then very quickly react thermally with the aldehydes in a regiospecific manner to give the 3-oxazolines 4. Azirines monosubstituted in position 2 (1b and 1c) give mixtures of cis,trans-oxazoline isomers, in which the cis isomer predominates. The stereoselectivity of the cycloaddition reaction can be rationalized by a simple model (scheme 10). The stereoisomeric 3-oxazolines 4 are distinguishable in the NMR spectra by the large homoallylic coupling constants between the H atoms on C(2) and C(5).