The water/base intolerance of the previously reported electrophilic phosphonium cations has been overcome by replacing the labile electron-withdrawing groups generally attached to phosphorus (e.g. -F, -OAr, -CF3) with methyl groups. Tri-phosphorus(v) tricationic species, accessible in one-pot from commercially available materials, are air and water/base tolerant, yet are sufficiently Lewis acidic for catalysis.