Eight new p-hydroxybenzoic acid (PHB) and poly(ethylene terephthalate) (PET) copolymers containing vanillic acid (VA), p-aminobenzoic acid, m-hydroxybenzoic acid, hydroquinone/terephthalic acid (TPA), bisphenol A/TPA, 1,5-naphthalenediol/TPA, 2,7-naphthalenediol/TPA, and. 1,4-dihydroxyanthraquinone/TPA as eight third monomers with a variety of structural features were synthesized by melted-state copolycondensation and were characterized through a thermal analyzer, proton nuclear magnetic resonance, wide-angle X-ray diffraction (WAXD), and a scanning electron microscope (SEM). The experimental results show that PHB/PET/VA copolymers exhibit a faster polycondensation rate, lower melting temperature, and higher thermostability than do the other seven copolymers and third monomer-free PHB/PET polymers. The as-spun fibers derived from the PHB/PET/VA copolymers with different VA contents show tensile strengths, Young’s moduli, and break elongations of 0.6-1.5 GPa, 28-67 GPa, and 7-9%, respectively. A highly oriented fibrillar structure in the PHB/PET/VA copolymer fibers was observed using WAXD and SEM. The most effective third monomer of the eight third monomers for an enhancing polycondensation rate and molecular weight of the PHB!PET polymers and for improving their thermal and mechanical properties is found to be vanillic acid (VA).