A liquid crystalline epoxy resin of p-biphenylene di-4-(2,3-epoxypropyloxy)benzoate (p-BDEPB) was synthesized from allyl bromide, 4-hydroxy ethyl benzoate and 4,4-dihydroxybiphenyl. Its structure and liquid crystalline behavior were characterized by DSC, 1H-NMR, FTIR, POM and XRD. The results are shown that this compound is smectic liquid crystalline.The melting point of p-BDEPB is 210 oC and clearing point is over 300 oC, the epoxy value is 0.312 mol/100g. The average curing Ea of p-BDEPB/3-methyl-tetrahydrophthalic anhydride (MeTHPA) system is 97.2kJ/mol. The gel point of cured-system Tgel is 89.0 oC, curing temperature Tcu is 132.5 oC and finishing temperature Tf is 146.5 oC. The curing reaction can be described by the autocatalytic Šesták-Berggren (S-B) equation, the two reaction orders m and n is 0.23 and 0.74, respectively.