A series of homopoly(ester-imide)s was prepared by polycondensation of alpha,omega-dihydroxyalkanes and the dichloride of 4-aminocinnamic acid trimellitimide. Upon moderate or rapid heating and cooling, the poly(ester-imide)s containing odd-numbered spacers form an enantiotropic highly viscous smectic-C phase and the solid state is a frozen smectic-C phase. The longest odd spacer (9 CH2 groups) enables crystallization upon annealing. All poly(ester-imide)s having even spacers form a monotropic, long-lived smectic liquid crystalline (LC) phase and a quasi-crystalline smectic-H phase in the solid state. The layer distance (d-spacing) of the smectic-H phase is considerably shorter than that of the smectic LC phase. The rate of crystallization (formation of the smectic-H phase) increases with the length of the spacer. C-13 NMR CP/MAS measurements suggest that the longest aliphatic spacers (greater than or equal to 12, 16, and 22 CH2 groups) can form an ordered paraffin phase between the "two-dimensional" crystals of the mesogens.