The syntheses of cyclo-[R2Sn(OPPh2O)(2)SnR2]-(O3SCF3)(2) (R = Me (1), t-Bu (2)) by the consecutive reaction of R2SnO (R = Me, t-Bu) with triflic acid and diphenylphosphinic acid are presented. In the solid state, 1 and 2 were investigated by Sn-119 MAS and P-31 MAS NMR spectroscopy as well as X-ray crystallography and appear to exist as ion pairs of cyclo-[R2Sn(OPPh2O)(2)SnR2](2+) dications and triflate anions. In solution, 1 and 2 are involved in extensive equilibria processes featuring cationic diorganotin(IV) species with Sn-O-P linkages, as evidenced by Sn-119 and P-31 NMR spectroscopy, electrospray mass spectrometry, and conductivity measurements.