First, 4,4-biphenol diglycidyl ether (DGEBP) with high epoxy value and high crystallinity was prepared by one-step precipitation reaction of 4,4-biphenol (BP) and epichlorohydrin (ECH). The structure of DGEBP was confirmed by FTIR and NMR, and the optimum process conditions were determined successively. POM and XRD measurements verified that DGEBP was a solid powdered epoxy resin with high crystallinity and did not have liquid crystal behavior. Six curing agents were selected to cure DGEBP, respectively, to form crosslinked networks, and all the as-prepared cured products had good thermal properties. And then, DGEBP was used to modify bisphenol-A epoxy resin/polyoxyphenol (PKHH) binary blend resin system with dicyandiamide (DICY) as the hardener to obtain multiple modified ones (BPx-BA-PKHH). DMA and mechanical property analysis showed that DGEBP unit in the cured networks exhibiteds liquid crystallinity, and mesogenic domains appeared. At the same time, the tensile strength (87.39 MPa), Modulus (2.76GPa), shear strength (19.38 MPa) and toughness of BPx-BA-PKHH were significantly improved. And, the best comprehensive performance was obtained at the addition amount of DGEBP by 5-7 phr.