Organophosphorus flame retardants (OPFRs) have been detected ubiquitously in the air and water worldwide, but no study has focused on their air-water exchange process. Here, we investigated the concentrations, distributions, and seasonal variations of OPFRs in the coastal air and water of Dalian, China. The total concentrations of 10 OPFRs in the air based on passive air sampling ranged from 0.50 to 20.0 ng/m³, while the concentrations of OPFRs in the water dissolved phase ranged from 48.3 to 681 ng/L. Relatively high concentrations were mainly discovered near the industry areas or river estuaries, suggesting that point sources along the coastline may significantly influence the local OPFR concentrations. Tris(2-chloroisopropyl) phosphate (TCIPP) was the most dominant congener followed by tris(2-chloroethyl) phosphate (TCEP), which was consistent with their high production and persistence. The air-water gaseous exchanges of OPFRs were estimated for the first time according to their concentrations in gaseous and dissolved phases. Generally, the gaseous exchange fluxes varied with sampling site and period. TCIPP showed the highest gaseous deposition flux of −395 ± 1211 ng/(m² d), while TCEP showed the highest emission flux of 1414 ± 2093 ng/(m² d). The dry deposition fluxes of OPFRs (0.05–822 ng/(m² d)) were also calculated based on their particle fractions in the air. The result suggested that both gaseous exchange and particle deposition processes significantly influenced the air-water transport of OPFRs in this area.