We report a novel technique for fabricating the heterogeneous double-ring-like structural array by colloidal lithography and two-step dewetting process. First, the 2D non-closed-packed (ncp) silica sphere arrays were obtained by lift-up lithography. Then, the ncp sphere array transferred onto the Rhodamine B (RB)@poly(vinyl alcohol) (PVA) film was used for the mask during reactive ion etching (RIE) process. Sequentially, the substrate with RB@PVA ring-like structure arrays under the silica sphere was dip-coated from poly(N-vinylcarbazole) (PVK) chloroform solution with certain concentration. Due to the presence of ordered 2D sphere arrays, the two-step dewetting behavior happened on top of the sphere and the silicon wafer between adjacent spheres, respectively. After removing the silica sphere arrays by hydrofluoric acid, the RB@PVA/PVK heterogeneous double-ring-like structure array was exhibited on the substrate. We characterized this particular structure by SEM, AFM, and fluorescence spectrum, which prove that both the inner RB@PVA ring and outer PVK ring are independent without any reaction. Accordingly, this method could be extended to other materials owing to its universality. These unique structural arrays have potential application in optoelectronic devices, surface photocatalysis, and surface enhanced Raman scattering (SERS).