Tris[2-(2-pyridyl)ethyl]phosphine chalcogenides, prepared easily from 2-vinylpyridine and phosphorus red, react chemoselectively with three equivalents of 4-toluenesulfonic or trifluoromethanesulfonic acids under mild conditions (THF, r.t., 50-80 min, THF) to give the corresponding tri(pyridinium) triflates and tosylates in quantitative yields.