The triboelectric nanogenerator (TENG) has been invented as an important mechanical energy harvesting technology, but the further improvement of its triboelectric properties is still required to meet those of practical and functional devices. The tribo-charge surface density of contact materials is considered to be crucial for the performance of TENG. However, currently the enhancement of the tribo-charge surface density is realized either by the physical modification or by the chemical modification of triboelectric surfaces. Here, to maximize the output performance, we introduce a novel post-processed micro-patterned double-network polydimethylsiloxane triboelectric film, in which both chemical modification and physical modification are simultaneously realized in one step along with high controllability, for the first time. With rational selection of monomers and photo-masks, the V_oc and J_sc values of the TENGs are enhanced 17.4 times and the output power is significantly enhanced by ∼189 times compared to the devices without modification. This is associated with the improved surface potential and contact area of the triboelectric layer, leading to enhanced tribo-charge surface density and subsequent enhanced device performance. Moreover, the fabricated TENG exhibits high sensitivity. This design principle offers a universal method to further improve the device performance of TENGs in a low-cost, rapidly yielding way.