Abstract P-Methyl-and P-phenylphosphaethene were generated in solution under very mild conditions in virtually quantitative yield by a thermally-induced extrusion of the phosphorus- containing bridge from appropriately substituted 2-phosphabicyclo [2.2. 2] octa-5, 7-dienes. The phosphaethenes so formed, the simplest yet produced by conventional methods, are trapped readily in [2+ 4] cycloadditions with conjugated dienes.