Reaction of 2,6-xylyl isoselenocyanate (1) with organolithiumcompounds was examined focussing on the siteselectivities. Phenyllithium attacked selenium exclusively whereas some benzylic organolithiums reacted at the central carbon of 1 to afford the corresponding lithium selenocarboximidates. Phenylethynyllithium and tBuLi gave mixtures of the carbophilic and selenophilic products. The lithium enolate