Naphthalene is the most abundant polycyclic aromatic hydrocarbon (PAH) in vehicle emissions and polluted urban areas. Its atmospheric oxidation products are oxygenated compounds that are potentially harmful for health and/or contribute to secondary organic aerosol (SOA) formation. Despite its impact on air quality, its complex structure and a lack of data mean that no detailed scheme of naphthalene gaseous oxidation for SOA formation and speciation has been established yet. This study presents the construction of the first near-explicit chemical scheme for naphthalene oxidation by OH, including kinetic and mechanistic data. The scheme redundantly represents all the classical steps of atmospheric organic chemistry (i.e., oxidation of stable species, peroxy radical formation and reaction, and alkoxy radical evolution), thus integrating fragmentation or functionalization pathways and the influence of NOx on secondary compound formation. Missing kinetic and mechanistic data were estimated using structure–activity relationships (SARs) or by analogy with existing experimental or theoretical data. The proposed chemical scheme involves 383 species (231 stable species, including 93 % of the major molar masses observed in previous experimental studies) and 484 reactions with products. A first simulation reproducing experimental oxidation in an oxidation flow reactor under high-NOx conditions shows a simulated SOA mass on the same order of magnitude as has been observed experimentally, with an error of −9 %.