Black phosphorus (BP) is a two-dimensional (2D) semiconductor that has recently attracted much interest due to its unique characteristics. However, BP is susceptible to oxidization under ambient conditions. In this work, a facile one-step route is presented, in which stable P-C bonds were formed by ball milling bulk BP and multi-walled carbon nanotubes (MWCNTs) mixture without any additives. The BP-MWCNTs hybrid and the milled BP (m-BP) were both dispersed in water under ambient conditions, and their optical absorbances were monitored. The resulting data showed that the absorbance value of the BP-MWCNTs hybrid decreased by 10.87% after 5 d, whereas the m-BP decreased by 59.21%. Surprisingly, the BP-MWCNTs hybrid also exhibited ultrahigh photocatalytic activity in the visible light range. Within 60 min of irradiation, the removal efficiency of rhodamine B (RhB) by the BP-MWCNTs hybrid reached 88.42%, which is four times higher than that of the bare m-BP. This improvement can be attributed to the formation of the P-C bond and the enhanced surface adsorption capacity resulting from the introduction of the MWCNTs, indicating that the utilization of the charges on the surface of the photocatalyst is further improved. In short, this study not only provides an easy method to synthesize the stable BP-based material for practical applications but also represents a new approach to enhance the photocatalytic activity of BP.