In the presence of a catalytic amount of Ni(cod)(2) (cod = 1,5-cyclooctadiene) and PCy3 (Cy = cyclohexyl), the cross-tetramerization of tetrafluoroethylene (TFE), alkynes, and ethylene occurred in a highly selective manner to afford a variety of 1,3-dienes with a 3,3,4,4-tetrafluorobutyl chain. In addition, a Ni(0)-catalyzed cross-tetramerization of TFE, alkynes, ethylene, and styrenes was developed. These catalytic reactions might proceed via partially fluorinated five- and seven-membered nickelacycle key intermediates.