The molecular order and thermotropic transitions of tris-cis-tris-trans-dodeca[organo(dimethylorganosiloxy)]cyclododecasilox anes {RSi(O) [OSiMe2R']}(12) (R = Ph, R' = Me, CH2Cl, Vi; R = Me, Et, Vi, R' = Me) have been investigated using differential scanning calorimetry, thermogravimetric analysis, and X-ray scattering. The cyclododecasiloxanes with phenyl side groups (R = Ph) can form mesomorphic structures within a very wide temperature range. Compounds with R = Me and Vi are liquids and exhibit microphase separation above their glass transition temperature because of the different nature and structure of the organic R and trimethylsiloxy OSiMe3 side groups. When the side group R = Et, a mesomorphic structure is formed in a substantially more narrow temperature region than that for cycles containing phenyl groups. Thus, the type of side group R in organocyclododecasiloxanes determines their ability for self-ordering into mesomorphic structures and the thermal stability of the mesomorphic state.