Alkynylxenon(II) fluorides, RC=-CXeF, have been prepared from the reactions of the corresponding trimethyl(alkynyl)silanes, Me-3- SiCdropCR, and XeF2 in the presence of [NMe4]F in common organic solvents at low temperature. The existence of the linear unit CdropC-Xe-F was proved for PhCdropCXeF by the F-19-C-13 NMR correlation method using the HMBC pulse sequence.