Reaction of alkyl isocyanides, phenyl vinyl selenone, and water in the presence of a catalytic amount of Cs2CO3 afforded oxazolidin-2-ones in good yields. This unprecedented heteroannulation process created four chemical bonds in a single operation with the isocyano group acting formally as a polarized double bond and phenyl vinyl selenone as a latent 1,3-dipole. The phenylselenonyl group played a triple role as an electron-withdrawing group to activate the 1,4-addition, a leaving group, and a latent oxidant in this transformation.