Combining electro-oxidation (EO) with biodegradation for real oil sands process water (OSPW) treatment was evaluated in terms of naphthenic acid (NA) biodegradation enhancement. Ion mobility spectrometry (IMS) qualitative analysis showed that EO by graphite was able to degrade the different NA clusters in OSPW including: classical, oxidized and heteroatomic NAs. Applying EO even at current density as low as 0.2 mA/cm2 was still able to reduce classical NAs and acid extractable fraction (AEF) by 19% and 7%, respectively. EO pretreatment preferentially broke long carbon chains and highly cyclic carboxylic fractions of NAs in OSPW to improve the biodegradation of NAs. Aerobic biodegradation for 40 days reduced NAs by up to 30.9% when the samples were pre-treated with EO. Applying EO at current densities below 2 mA/cm2 maintained current efficiency as high as 48% and resulted in improvement in the biodegradation rate of remaining NAs by up to 2.7 folds. It was further revealed that applying EO before biodegradation could reduce the biodegradation half-life of classical NAs by up to 4.4 folds. 16S amplicon sequencing analysis showed that the samples subjected to biodegradation had increased abundances of Sphingomonadales and Rhodocyclales with increasing applied current density for EO pre-treatments. Copyright © 2020 Elsevier B.V. All rights reserved.