Polycyclic aromatic hydrocarbons (PAHs) are toxic pollutants that exist extensively in the environment. Microbial degradation is the main pathway of PAHs eradication in natural environment and therefore is of importance to investigate. Advancement has been made in recent years regarding the PAHs molecular degradation mechanisms in bacteria. In this review, we summarized some of the research progresses in microbial PAHs biodegradation pathways (including salicylate pathway and protocatechuate pathway), key enzymes (nah-like, phn, phd, nid and nag) and genes involved. Emphasis was given on naphthalene and phenanthrene which were often used as the representatives of PAHs. It is likely that the new information will promote further research and applications of microbial PAHs biodegradation technology.