In order to improve the processability of rigid rod-like polyspiroacetals without significant loss of their good nature, in this work a few new ideas for molecular design were adopted: (1) Copolymerization for breaking the regularity of polymer repeating units. (2) Incorporation of flexible methylene linkages or spacers in rigid spiroacetal polymer main chain. (3) Derivatization of long flexible side chains onto rigid polymer backbone. On the basis of these ideas, a series of polyspiroacetals were prepared, using the phase transfer catalyst, BTMAC, by interfacial polymerization reactions of spiroacetal monomer (SAB) and disubstituted aromatic acid chlorides or aliphatic diacid chlorides. Physical properties of these polyspiroacetals are discussed in relation to their chemical structure and are compared with those of polyspiroacetals synthesized by several other researchers.