Metal-doped nickel cobalt based-phosphides are an effective method to improve electrochemical performance. This work aims to prepare nickel cobalt based-phosphides based on VIB group elements (M = Cr, Mo, W)-doped nickel cobalt hydroxides precursors. The influences of different mass of metal salts loading into phosphides on the electrochemical performance are investigated. The results show the flower shape morphology for all samples. Further, the excellent specific capacitances are to be 1839, 1599 and 1786 F g−1 for NiCoCr phosphides (NCCP), NiCoMo phosphides (NCMP) and NiCoW phosphides (NCWP), respectively, higher than pristine NiCo phosphides (NCP, 1128 F g−1) at 1 A g−1. In addition, the assembled supercapacitor device can reach maximum energy density of 29 Wh kg−1 with excellent capacitance retention.