Relatively low rate of electron recovery is one of the factors that limit the advancement of bioelectrochemical systems. Here, new periodic polarizations were investigated with electroactive biofilms (EABs) enriched from activated sludge and Geobacter sulfurreducens biofilms. When representative anode potentials (E a ) were applied, redox centers with midpoint potentials (E mid ) higher than E a were identified by localized cyclic voltammetry. The electrons held by these redox centers were accessible when E a was raised to 0.4 V (vs. Ag/AgCl). New periodic polarizations that discharge at 0.4 V recovered electrons faster than normal periodic and fixedpotential polarizations. The best-performing periodic step polarization accelerated electron recovery by 23%−24% and 12%−76% with EABs and G. sulfurreducens biofilms, respectively, compared to the fixed-potential polarization. Quantitative reverse transcription polymerase chain reaction showed an increased abundance of omcZ mRNA transcripts from G. sulfurreducens after periodic step polarization.Therefore, both the rate of energy recovery by EABs and the performance of bioelectrochemical systems can be enhanced by improving the polarization schemes.