Graphene-based hybrid composites as positive electrodes have aroused great interest in the field of hybrid supercapacitors. However, the charge storage capability of hybrid composites suffers from the scarce interaction between their end members to some extent. Herein, a hybrid composite with electrostatic interaction was obtained by employing a heterogeneous assembly strategy of Ni–Co layered double hydroxide (LDH) and sulfonated graphene nanosheets (SGN). Depending on the substitution of the negatively charged SGN for the interlayer nitrate anions compensating for the positively charged LDH host slabs, the abundance of Ni³⁺ on the surface of the hybrid composite could be increased to intensify the electrostatic interaction within hybrid composites. As expected, the effective coupling of LDH with SGN ensured the uniform incorporation of heterogeneous components. The unique structure of the hybrid composite accelerated electron transfer and ion diffusion processes during electrochemical reactions, which is beneficial to improve the electrochemical performance of battery-type electrodes. Further evaluation showed that the specific capacity of the LDH/SGN hybrid composite is 1177 C g⁻¹ (2354 F g⁻¹) at 1 A g⁻¹. Additionally, the LDH/SGN//AC hybrid supercapacitor achieved an energy density of 43 W h kg⁻¹ at 800 W kg⁻¹ and still retained 94% of its initial specific capacitance over 10 000 cycles. The boosting effect of the electrostatic interaction within the hybrid composite on electrochemical properties offers a novel pathway for the development of supercapacitors.