A novel three-dimensional ordered layer-by-layer graphene oxide/copper phthalocyanine polymer (GO/CuPc) films were fabricated by the orientational ordering in liquid crystal (LC) dispersions and immobilization of ordered structure upon casting and drying. The results of POM, UV-vis and EIS indicated that the prolongation of standing days and the increase of GO concentration effectively promote the self-assembly of CuPc and the formation of LC GO/CuPc dispersions. And the GO/CuPc (2:1) dispersions exhibited strongly self-assembly behavior of CuPc by using GO as template and remains excellent texture of liquid crystal. By simple casting and drying, the long range orientation and alignment of GO/CuPc films can be successfully immobilized, which drastically enhanced the dielectric constant of GO/CuPc. Compared with the disordered GO/CuPc (2:1), the dielectric constants at 1 KHz and 100 KHz reach 164.82 and 31.95, leading to an increment of 319% and 275%, respectively.