Polylactic acid (PLA) is a widely recognized biodegradable polymer. However, the slow crystallization rate of PLA restricts its practical applications. In this study, camphor leaf biochar decorated with multi-walled carbon nanotubes (C@MWCNTs) was prepared using the strong adhesive properties of polydopamine, and PLA/C@MWCNTs composites were fabricated via the casting solution method. The influence of C@MWCNTs as a novel nucleating agent on the melt behavior and non-isothermal crystallization behavior of PLA was investigated using differential scanning calorimetry (DSC). The crystallization kinetic parameters were obtained through the Jeziorny, Ozawa, and Mo methods, and the crystallization activation energy of the PLA/C@MWCNTs composites was calculated by the Kissinger method. The results show that the PLA/C@MWCNTs composites exhibit higher crystallinity and crystallization temperatures than those of PLA. Non-isothermal crystallization kinetic analysis reveals that the Mo method better describes the non-isothermal crystallization kinetics of both PLA and PLA/C@MWCNTs composites. In addition, it was found that C@MWCNTs, despite increasing the crystallization activation energy, can act as an efficient nucleating agent to increase the crystallization rate of PLA. These experimental results provide valuable insights for enhancing the slow crystallization rates associated with PLA.