The biodegradation of benz[cdanthracene (BaA), which was a high-molecule-weight PAH, was enhanced via a combination of alkaline and alkyl polyglucosides (APG) treatment during waste activated sludge (WAS) anaerobic fermentation. The biodegradation efficiency of BaA was increased from 14.1% in the control to 30.2 and 47.8% in pH 10 and pH 10 & APG reactors, respectively. Mechanism investigations found that the alkaline and APG treatments stimulated the processes of BaA desorption from sludge and transfer/entry into microorganisms, and ultimately improved the BaA bioavailability. Meanwhile, the huge released substrates from WAS not only served as carbon sources but also involved in the electron transfer among microorganisms which contributed to the BaA biodegradation process. Moreover, the microbial activities involved in BaA biodegradation, including the abundances of functional bacteria, activities of enzymes and quantities of genes, were also incremented due to the alkaline and APG treatments. Overall, the simultaneous improvement of BaA bioavailability and microbial activities enhanced its biodegradation efficiency.