A new class of chiral liquid-crystalline polysiloxanes was synthesised, and their thermotropic behaviour and mesophase structure were investigated. The mesogenic side chains consisting of a three-phenyl core were connected to the siloxane polymer backbone by an alkylene spacer segment of varying number m of methylene units and of a chiral sulphide substituent. An X-ray diffraction study of powder and fibre specimens permitted to elucidate the structure of the mesophases, which in any case resulted in tilted, monolayer types. Polysiloxanes P8, P10 and P11 incorporating longer spacers with m = 8, 10, and 11, respectively, exhibited a rich variety of smectic mesophases. The smectic I-smectic F-smectic C phase sequence with rising temperature was identified in all three samples by analysis of the wide-angle diffraction. Three-dimensionally ordered structures were also formed at low temperatures. The various low-angle reflections on the smectic layers were used to evaluate the projections of the electron density profiles along the layer normal, and the most physically acceptable profiles were selected from the numerous possibilities for each smectic mesophase.