MFC anodic denitrification is more suitable for the coexistence of organic matter and nitrate in actual sewage, but the traditional carbon source has some problems such as high cost and difficulty of dosage control in MFC. Herein, corncob and polycaprolactone (PCL) were mechanically pulverized and mixed in the system of polyvinyl alcohol and sodium alginate, and cross-linked to prepare slow-release carbon source fillers (CPSP), which were added to the MFC anolyte to realize the coupling of solid-phase denitrification and anodic denitrification. Results showed the start-up period of MFC experimental group (MFC-C) with CPSP was slightly longer than the control group (MFC-0), but MFC-C's maximum output voltage (648.4 mV) and power density (2738 mW/m3) could be increased by 5% and 15% higher than that of MFC-0 (P < 0.05). The degradation process of MFC substrate in unit cycle was mainly divided into nitrogen removal stage (0–8 h) and electricity generation stage (8–48 h). The NO3−-N and COD degradation and power generation kinetic processes of MFC conformed to the Han-Levenspiel model. Kinetics experiments showed CPSP can improve the affinity and tolerance of MFC to NO3−-N, also it can alleviate the pressure of electron competition in anolyte and improve coulombic efficiency. In addition, microbial communities were significantly changed under the effect of CPSP (P < 0.001). Meanwhile, CPSP can promote the synthesis of denitrification functional genes. This study provides a new strategy to improve the performance of MFC by the addition of novel denitrification carbon source.