High mountains may serve both as condenser for vapor phase persistent organic pollutants (POPs) and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs along altitudinal profiles is of interest in understanding the role of high mountains in the atmospheric transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in a selected moss species, Hypnum plumaeformae WILS, from two altitudinal profiles on the northern slope of Nanling mountains in Southern China were analyzed and compared with those in air samples. The total PAH concentration in the mosses was 310–1340 ng g−1 dry weight, with phenanthrene being the most abundant. The distribution patterns of PAHs in the moss samples matched well with those in bulk atmosphere deposition in the adjacent source areas. The PAH distribution pattern in the mosses was a composite of both particle-associated and vapor phase PAHs, with heavy PAHs are susceptible to uptake/retention by mosses than light PAHs. A plot of log (Cmoss/Cair) against log Koa gave a good linear relationship in the log Kao range of 6.7–10.2. It is suggested that the widely spread moss, H. plumaeformae WILS, can be used as an effective tool in the biomonitoring of atmospheric PAHs pollution in East Asia. The concentrations of most PAHs in the mosses generally declined with increasing altitude. In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation are proposed as the major mechanisms for the compositional fractionation of PAHs along the altitudinal profile.