To further understand the toxic effects of Phthalate Esters (PAEs) on electroactive biofilms (EABs), based on summarizing the current distribution situation of PAEs in natural water and wastewater treatment systems, this review analyzed the influence mechanism of PAEs and other toxic substances on biofilms, and proposed the potential influence mechanism of PAEs on the performance of EABs. The influence mechanism mainly includes three aspects: the influence on the colonization of electroactive microorganisms, the influence on succession of electroactive biofilms, and the influence on functions of electroactive biofilms.