The emerging thick electrode concept is dedicated to maximize active material areal loading at the device-scale through straightforward structural designs to meet the high energy density demand. Nevertheless, overcoming the sluggish charge kinetics and complex manufacturing route in thick composite electrodes is still challenging. Herein, a novel all-laser structural engineering protocol is developed to construct MnO-Mn3O4/MnS heterostructure-anchored 3D porous graphene architecture with reinforced carbon nanotube (CNT) interface (MHGC) by layer-by-layer laser induction of polyethersulfone film containing manganese acetate precursors without introducing any templates or catalysts. Creatively, along with the synchronous generation of porous graphene and multivalent manganese compounds heterostructures, a uniform distribution process of nanoparticles is integrated into a one-step in-situ laser irradiation, which is unique and straightforward for preparing thick composite electrodes. Besides, the interlayer bridging of CNT network between MnO-Mn3O4/MnS/graphene layers accelerates electron transport, accompanied by the ameliorative deep diffusion of ions by open graphene macropores derived from laser-assisted vaporization. Thanks to the configuration of efficient electronic bridge and ion channel, combined with multi-heterointerface and fast surface reaction kinetics endowed by heterostructure nanoparticles, MHGC electrode with a thickness of 442 μm delivers a high specific capacitance of 954.5 mF cm−2 (at 0.5 mA cm−2). The assembled symmetrical supercapacitor with LiCl aqueous electrolyte exhibits a broadened potential window of 1.3 V, obtaining a prominent energy density (39.99 μWh cm−2) and power density (1625 μW cm−2). This advanced laser engineering and enabled thick electrodes open a brand-new avenue in burgeoning energy chemistries, not limited to supercapacitors and rechargeable batteries.