The geometric arrangement of liquid crystalline poly(dodecene sulphone)s containing cholestanyl pentenoic ester chemically bonded in the side-chains was characterized by monitoring the triplet transport via both steady-state emissions and decays of delayed fluorescence and phosphorescence. The increase in the mesogenic cholestanyl pentenoic side-chains shows an increase in the heterogeneity exponent or degree of disorder, h, which is greater than zero, suggesting that the explored system exhibits the non-classical diffusion-limited or fractal-like transport. The value of h is highly sensitive to the ratio of mesogenic to olefinic side-chains.