Pentelidene complexes of the type [Cp*E{W(CO)₅}₂] (Cp* = C₅Me₅; 1a: E = P, 1b: E = As) were reacted with the dichalcogenides R₂Ch₂ (R = Ph, Mes, Tipp; Ch = S, Se, Te; Mes = 2,4,6-trimethylphenyl; Tipp = 2,4,6-triisopropylphenyl) and the chalcogenols PhChH (Ch = S, Se). It has been shown that the formation of new E–Ch bonds proceeds under elimination of the Cp* substituent. The resulting chalcogenopentelidene complexes, which have been isolated and fully characterised, represent a novel class of phosphinidene complexes which can be synthesised through this general synthetic route.