Six varieties of liquid-crystalline side-chain polymers, poly (cholesteryl ω-(methacryloyloxy)alkanoates) (p-ChMO-n, n= 1,2,3,4,5,7, the carbon number of the alkyl chain), were studied by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS). On and after the first cooling run from the isotropic state, these polymethacrylates gave the same smectic phase. However, on the first heating run for virgin samples, unique phenomena were observed, similar to those frequently observed on the first heating run for thermotropic liquidcrystalline polymers. The thermal properties of the first heating run for these six polymers showed different tendencies betweenpChMO-n (n-1–3) andpChMO-n(4–7). Although the DSC curve ofpChMO-n (n= 4, 5 and 7) exhibited the melting and clearing points on the first heating run, the DSC curve ofpChMO-n (n= 1,2 and 3) exhibited an exothermal peak between the glass transition and the clearing point on the first heating run. This difference, probably due to the difference in the spacer length of these polymers, was investigated quantitatively by small-angle X-ray scattering by which the micro-change of the packing structure of the side chains of the polymers was traced.