A high dielectric constant nano-composite was fabricated using polyurethane (PU) as matrix and poly (p-chloromethyl styrene) (PCMS) grafted with copper phthalocyanine oligomer (CuPc, a planar multiring semiconductor with dielectric constant>105) (name the grafting product as PCMS-g-CuPc) as filler. According to the TEM-observed morphologies, PCMS-g-CuPc balls (~80 nm) distribute uniformly in PU matrix, while in PCMS-g-CuPc balls the PCMS acts as “matrix” which contains dispersed CuPc particles with a average size of ca. 25nm [1/20 of that of CuPc in simple blend of PU and CuPc (PU/CuPc)]. At 100Hz, the dielectric constant of the nanocomposite reaches 345, almost 7 times higher than that of PU/CuPc. The enhanced dielectric response in the nano-composite can be explained by the remarkably strengthened interface exchange coupling effect as well as the Maxwell-Wagner-Sillars polarization mechanism due to the significantly reduced CuPc particle size in the nano-composite.