Transition metal selenides have excellent promise for high-performance electrode materials owing to their great electrical conductivity and theoretical capacity. Unfortunately, the electrochemical performance of single-metal selenides is undesirable because of their low energy density and poor cyclic stability, and one practical approach is to introduce heteroatoms to create bimetallic selenides. Herein, a novel bimetallic NiCo2Se4/Fe2CoSe4 chrysanthemum flower assembled by nanosheets on NiF was synthesized via a hydrothermal process as a binder-free electrode for a hybrid supercapacitor. Because of the presence of plentiful redox active sites, unique architecture with large surface area and mesoporous channels, desirable electrical conductivity, and synergistic effect of Ni, Co, and Fe, the bimetallic NiCo2Se4/Fe2CoSe4 electrode material shows significantly increased electrochemical performance. Interestingly, the bimetallic NiCo2Se4/Fe2CoSe4 electrode material shows an outstanding specific capacity of 323.66 mAhg−1 (1175.97 Cg−1) at 1 Ag−1, retaining 91.08% of the initial capacity at 20 Ag−1, with long-lasting cyclic stability of 91.08% after 10,000 GCD cycles at 20 Ag−1. A binder-free bimetallic NiCo2Se4/Fe2CoSe4 @NiF electrode's outstanding electrochemical efficiency can be related to the existence of two bimetallic selenides, and beneficial interaction, which yields quick charge transfer reactions. Moreover, the NiCo2Se4/Fe2CoSe4@NiF//AC@NiF hybrid supercapacitor by bimetallic NiCo2Se4/Fe2CoSe4@NiF (positive electrode) and activated carbon (AC@NiF, negative electrode) displayed specific energy which is 51.83 Whkg−1 at 749.83 Wkg−1 and 34.2 Whkg−1 at 14996.34 Wkg−1 at 20 Ag−1 and superior stability of 92.33% after 10,000 GCD cycles. This research provides some insight into the design of an electrode material with a flower-like decorated with nanosheets morphology for hybrid supercapacitors.