Thirteen copolymers of the type (R2Si)n(R’2Si)m have been synthesized, where R, R’ = n-hexyl, n-pentyl, n-butyl, n-propyl, ethyl, and methyl, and R not-equal R’. The H-1 and Si-29 solution NMR spectra and thermal (DSC) transitions were measured for the copolymers and compared with those for the corresponding homopolymers. The composition (n/m ratio) was obtained from solution NMR and pyrolysis-GC/MS. The distribution of comonomers along the polymer backbone was determined by calculations from the pyrolysis-GS/MS results and found to be mostly random in nature.