Rational regulation of electrode materials with high conductivity and unexceptionable cycling stability is crucial to meet the requirements of high-performance supercapacitors (SCs). Herein, a hierarchical porous kebab-like heterostructure (CoNiFe-Se) is prepared by a facile solvothermal reaction and selenization step. Both experimental and computational results demonstrate that incorporating Se via hydrothermal reaction contributes to modulating the morphology and electronic structure of transition metal carbonate hydroxides. The heterostructured electrode with abundant active sites composed of electroactive polymetallic-CoNiFe imparts excellent charge storage. Additionally, the unique structure of CoNiFe-Se with its heterogeneous interface, oxygen vacancies and cavities improves electrochemical activity, accelerates electron transfer and suppresses the volume expansion during the cycling. As a result, the CoNiFe-Se exhibits excellent electrochemical performance of 5040 mF cm⁻² at 1 mA cm⁻² and long-term durability with 85.7% retained capacitance after 10 000 cycles. Interestingly, an integrated asymmetric supercapacitor performs well for energy storage. This finding opens a new avenue for developing transition metal carbonate hydroxides using selenization strategies in the field of SCs.