Conductive 2D metal–organic frameworks (MOFs) have merits beyond traditional MOFs for electrochemical applications, but reports on using MOFs as electrodes for electrochemical microsupercapacitors (MSCs) are practically non-existent. In this work, a Ni-catecholate-based MOF (Ni-CAT MOF) having good conductivity and exhibiting redox chemistry in the positive and negative voltage windows is developed. A novel process is developed to selectively grow the conductive Ni-CAT MOF on 3D laser scribed graphene (LSG). The LSG with its superior wettability serves as a functional matrix-current collector for the hybridization of conductive Ni-CAT MOF nanocrystals. Impressively, MSCs fabricated using the hybrid LSG/Ni-CAT MOF show significant improvement compared with MOF-free LSG electrodes. Specifically, the LSG/Ni-CAT MOF electrodes can deliver MSCs with a wide operating voltage (1.4 V), high areal capacitance (15.2 mF cm−2), energy density (4.1 µWh cm−2), power density (7 mW cm−2), good rate performance, and decent cycling stability. This work opens up an avenue for developing electrochemical microsupercapacitors using conductive MOF electrodes.