Capping represents an efficient and well-established practice to contain polycyclic aromatic hydrocarbons (PAHs) in sediments, reduce mobility, and minimize risks. Exposure to PAHs can encourage biodegradation, which can improve the performance of capping. This study investigates biodegradation of naphthalene (a model PAH) in highly reducing, sediment-like environments with amendment of different capping materials (PAC and sand). Microcosms were prepared with sediment enrichments, sulfate as an electron acceptor, and naphthalene. Results show that PAC stimulates naphthalene biodegradation and mineralization, as indicated by production of 14CO2 from radiolabeled naphthalene. Mineralization in PAC systems correlates with the enrichment of genera (Geobacter and Desulfovirga) previously identified to biodegrade naphthalene (Spearman's, p < 0.05). Naphthalene decay in sand and media-free systems was not linked to biodegradation activity (ANOVA, p > 0.05), and microbial communities were correlated to biomass yields rather than metabolites. Naphthalene decay in PAC systems consists of three stages with respect to time: latent (0–88 days), exponential decay (88–210 days), and inactive (210–480 days). This study shows that PAC amendment enhances naphthalene biodegradation under strictly sulfate-reducing conditions and provides a kinetic and metagenomic characterization of systems demonstrating naphthalene decay.