Three combined main-chain/side-chain liquid-crystalline polymers (MCSCLCPs) were prepared via hydrogen bonding or ionic interactions. The first MCSCLCP, PyHQ12-7CNCOOH, was prepared via hydrogen bonding between the pendent nonmesogenic pyridyl group in a main-chain liquid-crystalline polymer (PyHQ12) and the carboxylic acid group (-COOH) in mesogenic 8-[(4-cyano-4-biphenyl)oxy]octanoic acid (7CNCOOH). The second MCSCLCP, PABP-AA, was prepared via hydrogen bonding between the nonmesogenic azopyridyl group in the side chain of a main-chain liquid-crystalline polymer (PABP) and the carboxylic acid group (-COOH) in nonmesogenic p-anisic acid (AA). The third MCSCLCP, PABP-TSA, was prepared via ionic interactions between the nonmesogenic azopyridyl group in the side chain of PABP and the sulfonic acid group (-SO3H) in nonmesogenic p-toluenesulfonic acid (TSA). The presence of hydrogen bonds in self-assembled PyHQ12-7CNCOOH and PABP-AA and the presence of ionic interactions in PABP-TSA were confirmed using Fourier transform infrared (FTIR) spectroscopy, the thermal transitions in each MCSCLCP were determined using differential scanning calorimetry (DSC), and the mesophase structures of each self-assembled MCSCLCP were characterized using polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). The following observations have been made. Self-assembled PyHQ12-7CNCOOH (1) has a nematic mesophase as determined by POM, ( 2) undergoes a glass transition at ca. 54 degrees C and nematic-to-isotropic transition at ca. 154 degrees C as determined by DSC and WAXD, and (3) has a significant degree of hydrogen bonding at temperatures even above its clearing temperature as determined by in situ FTIR spectroscopy. Self-assembled PABP-AA (1) has a smectic mesophase as determined by POM and WAXD, (2) undergoes melting at ca. 120 degrees C and smectic-to-isotropic transition at ca. 161 degrees C as determined by DSC, and (3) has a moderate degree of hydrogen bonding at temperatures even above its clearing temperature as determined by in situ FTIR spectroscopy. Self-assembled PABP-TSA (1) has a smectic mesophase as determined by POM, (2) undergoes a glass transition at ca. 58 degrees C, melting at ca. 110 degrees C, and smectic-to-isotropic transition at ca. 155 degrees C as determined by DSC, and (3) has strong ionic interactions as determined by in situ FTIR spectroscopy at temperatures even above the clearing temperature.