Abstract The reaction of the pentaphenyphosphorus solvate Ph 5 P· 1/2PhH (I) with carboxylic and sulfonic acids was used to synthesize tetraphenylphosphonium carboxylates Ph 4 POC (O) R, R= C 6 H 4 (2-OH)(II), C 6 H 4 (2-COOH)(III), H (IV), Me (V), CCl 3 (VI), Ph (VII), PhCH= CH (VIII), CH 2 CH 2 C (O) OH (IX), CH= CHC (O) OH (X), and CH 2 C (O) OH (XI) and tetraphenylphosphonium sulfonates Ph 4 POSO 2 Ar, Ar= Ph (XII), C 6 H 4 Me 4 ( ...