Multiblock copoly(oxybenzoate-p-ethylene terephthalate) (POB-PET) was synthesized by a direct reaction of poly(hydroxybenzoic acid) (PHBA), acetoxybenzoic acid and poly(ethylene terephthalate). The synthesized multiblock POB-PET becomes more blocky and less soluble in the mixed solvent of trifluoroacetic acid and chloroform when the degree of polymerization of PHBA used in the synthesis is higher as evidenced in the solid-state and liquid-state nuclear magnetic resonance study. The thermal curves displayed by the synthesized multiblock 20/80 and 40/60 POB-PET contained distinctive contributions from both PET blocks and POB blocks in the copolymers when the degree of polymerization of PHBA used in the synthesis is seven. Only 20 mol% of POB is needed to form liquid crystalline phase in these multiblock POB-PET as opposed to a minimum of 40 mol% of POB is required to form liquid crystalline phases for random POB-PET.