Ultrahigh molecular weight polyethylene (UHMWPE) fiber has many outstanding properties. However, poor interfacial adhesion of the UHMWPE fiber/polymer matrix interface limits its applications as reinforcement in high performance polymer matrix composites. Therefore, a new thermosetting resin system, named PCH, which is only composed of carbon and hydrogen elements, has been developed according to law of similar mutual solubility and the structural characteristics of UHMWPE fiber. The adhesion property was investigated by mechanical properties test, thermal performance test, and polymer solution properties test. Test results show that a strong interaction occurs between UHMWPE fiber and the PCH matrix due to the structural and polar similarity. In the case of slight difference between solubility parameters of UHMWPE fiber and cured PCH resin, it is found that the wettability of PCH resin on surface of the fiber can be improved and the difference between the coefficients of thermal expansion of the matrix and the fiber decreases with the increase of styrene added into the PCH. An optimal interfacial adhesion can be obtained as the ratio of PCH/styrene is approximately 55/45.