Transphosphination reactions of (Me3M)3P and Me3MPH2 compounds (M = Si, Ge, Sn; Me = CH3) using HE(CF3)2 or H2ECF3 (E = P, As) yield derivatives of the types Me3ME(CF3)2, Me3ME(H)CF3, and (Me3M)2ECF3, respectively. The reactivity of the different systems depends on M (Si < Ge < Sn), E (P < As), and the phosphine [Me3MPH2 < (Me3M)2PH < (Me3M)3P]. Me3ME(H)CF3 compounds undergo dismutation forming (Me3M)2ECF3 and H2ECF3. Reactions of the new derivatives with polar compounds (HBr, H2E′CF3, Me3M′Br) result in cleavage of the M-E bond. Decomposition of the CF3E derivatives occurs by β-elimination of fluorine yielding Me3MF besides polymers of unknown structure.