In recent years, three-dimensional (3D) graphene has emerged as front runners to solve the restacking issues of two-dimensional (2D) graphene in the hope of achieving a high capacity in supercapacitors. Nevertheless, the traditional 3D graphene still reveals an unsatisfactory capacitance property on account of the simplex macropore structure and un-optimized surface properties; in addition, simultaneously optimizing structure as well surface properties by one-step procedure also faces significant challenges. Herein, formamide was inventively employed as a modulator of pore structure and meanwhile a dopant of nitrogen to ameliorate the surface properties. As expected, it has been found that the supercapacitor performance of optimized 3D nitrogen-doped graphene have been remarkably boosted compared with the traditional 3D graphene. An initial capacity of 275 F g^-1 at the current densities of 0.5 A g^-1 was achieved. Moreover, the few capacitance fade after 2000 charge–discharge cycles at a current density of 20 A g⁻¹ has been demonstrated. This work provided a new clue that how to design the porous graphene framework for supercapacitors and beyond with simple method.