(S)-Hexakis(4-(4′-(6-methyl)octyloxy)biphenoxy)cyclotriphosphazene (SMOCP) was synthesized in a search for new ferroelectric liquid crystalline compounds. We found an enantiotropic ferroelectric smectic C* phase between 419 and 441 K in SMOCP by using polarizing microscopy and DSC measurements. The spontaneous polarization was estimated to be -130.5 μCm−2at 437.6 K, several times larger than that of DOBAMBC ((S)-2-methylbutyl 4-(4′-decyloxybenzylidene)aminocinnamate.