This study aimed to enhance the efficiency of SBES in remediating polycyclic aromatic hydrocarbon (PAH)-contaminated soils by modifying the anode with laccase. The experiment involved four SBES anodes: a carbon nanotube-modified anode (CNT), a free laccase-modified anode (Lac), a gelatin-encapsulated laccase-modified anode (Lac-Gel), and a CaCO3 sustained-release microsphere-loaded laccase-modified (CaCO3-SMs@Laccase) anode (Lac-SMs). The CaCO3-SMs@Laccase notably extended the active period of laccase, with laccase activity in the Lac-SMs measured at 1.646 U/g after 16 days, which was significantly higher than the 0.813 U/g observed in the Lac-Gel group and the 0.206 U/g in the Lac group. The superior electricity generation and degradation efficiency observed in the Lac-SMs group were due to the sustained enzymatic activity provided by the CaCO3-SMs@Laccase. The prevention of anode acidification through CaCO3 decomposition, and promote the forward progress of electrochemical reactions. The phenanthrene (Phe) and pyrene (Pyr) removal efficiency in the soil of the Lac-SMs reached 90.78% and 84.72%, surpassing those of the Lac-Gel (80.36% and 79.14%), Lac (79.38% and 69.31%), and CNT (63.22% and 56.98%). The degradation pathway from Pyr to Phe was possible started with hydroxylation. In addition, the laccase also transformed the predominant microbial communities and metabolism pathways.