The interface bonding between black-phosphorus (BP) and polyaniline (PANI) is considered to be an important way to improve the electrochemical energy storage performance of PANI. However, polyaniline/black-phosphorus (PANI/BP) composites with good bonding relationship have not been explored for supercapacitor electrode materials. Here, we theoretically predicted the electronic structure and electron transmission direction of PANI/BP composites, and predicted that BP could enhance the electrochemical activity of PANI. Under the guidance of the theoretical prediction results, we prepared PANI/BP composite with good bonding structure and good dispersion (ABP-1.5) using hydroxylate BP (HBP, prepared by wet-ball-milling method) as carrier. Electrochemical test results exhibits that it has a specific capacitance of 962 F g−1 at 1 A g−1 in three-electrode system, which promote by 200% than that of PANI. In prototype device, ABP-1.5 displays specific capacitance of 864 F g−1 at 1 A g−1 and maintenance rate of 85% after 10,000 cycles at 3 A g−1. Its cycle life is also better than that of PANI (70%). The maximum specific energy of ABP-1.5 as the simulated supercapacitor can attain 28.1 Wh kg−1 at specific power of 112.4 W kg−1. Mechanism analysis shows that due to the surface activity and lamellar carrier characteristic of HBP, P-C bond and hydrogen bond induced by HBP contribute to the interface bonding and dispersion improving the electrochemical performance. This study provides ideas for further improving the energy storage performance of PANI.