The limited bioavailability of PAHs in non-aqueous phase liquid (NAPL) limits their degradation. The biodegradation of phenanthrene in n-tetradecane by hydrophilic bacterium Moraxella sp. CFP312 was studied with the assistance of two polymers, chitosan and carboxymethyl cellulose (CMC). Both chitosan and CMC improved the cell hydrophobicity of CFP312 and increased the contact angle of CFP312 cells from 30.4 to 78.5 and 88.5, respectively. However, CMC increased the degradation ratio of phenanthrene from 45 to nearly 100%, while chitosan did not cause any improvement. We found that CMC was more effective than chitosan in promoting CFP312 to stabilize Pickering emulsion. In the bacteria-CMC complex system, oil was dispersed into small droplets to obtain a high emulsification index and large specific surface area. Moreover, according to the microscopic image of the bacteria-CMC emulsion droplet, we observed that the droplet surface was tightly covered by the CFP312 cells. Therefore, CFP312 cells joined with CMC can utilize phenanthrene in oil phase at the oil-water interface. This study will offer a new strategy for effective microbial degradation of hydrophobic compounds in NAPLs by hydrophilic bacteria. KEY POINTS: • Biodegradation of phenanthrene in Pickering emulsions • Pickering emulsions stabilized by hydrophilic CFP312 joined with CMC. • Phenanthrene was degraded by CFP312 at oil-water interface.