A nitrogen-doped porous carbon/carbon nanotubes/graphene (PGMC) composite was prepared through a process of hydrothermal treatments, polymerization of o-phenylenediamine (OPD), and pyrolysis. The as-prepared PGMC composite was found to be of a nacre-like laminate porous structure, constructed with alternatively stacked two-dimensional (2D) graphene sheets and porous carbons, and also interspersed within one-dimensional (1D) multi-walled carbon nanotubes (MWNTs). The MWNTs effectively suppressed agglomeration of graphene sheets during the hydrothermal process and were interspersed in PGMC to help construct more networks with excellent conductivity. The PGMC possessed an enriched nitrogen doping ratio of 15.67 at% and relative high density of 1.39 g cm⁻³. The electrode composed of PGMC provided high gravimetric capacitance of 562.9 F g⁻¹ and volumetric capacitance of 782.4 F cm⁻³ at current density of 1 A g⁻¹, as well as excellent rate capability and cycling stability. The symmetric supercapacitors mounted with the as-prepared PGMC electrode were stably operated in a wide potential range of 0–1.3 V and demonstrated a superb gravimetric energy density of 19.79 W h kg⁻¹ at high power density of 650 W kg⁻¹, and a high volumetric energy density of 27.51 W h L⁻¹ with a power density of 904 W L⁻¹. The outstanding electrochemical performance enables this as-prepared nacre-like laminate PGMC composite to be a promising candidate for energy storage application.