The effect of natural organic matter (NOM) on toxicity and bioavailability of hydrophobic organic contaminants (HOCs) to aquatic organisms has been investigated with conflicting results and undefined mechanisms, and few studies have been conducted on volatile HOCs. In this study, six volatile chlorobenzenes (CBs) with 1-6 chlorine substitutions were investigated for their bioaccumulation in an acute toxicity to a green alga (Chlorella pyrenoidosa) in the presence/absence of Suwannee River NOM (SRNOM). The fluorescence quenching efficiency of SRNOM increased as the number of chlorine substitutions of CBs increased. SRNOM increased the cell-surface hydrophobicity of algae and decreased the release rates of algae-accumulated CBs, thus increasing the concentration factor (CF) and accumulation of the CBs in the algae. SRNOM increased the toxicity of monochlorobenzene and 1,2-dichlorobenzene, decreased the toxicity of pentachlorobenzene and hexachlorobenzene, and had no significant effect on the toxicity of 1,2,3-trichlorobenzene and 1,2,3,4-tetrachlorobenzene. Relationships between the 96h CF/IC50 (i.e., the CB concentration leading to a 50% algal growth reduction compared with the control) and physicochemical properties of CBs with/without SRNOM were established, providing reasonable explanations for the experimental results. These findings will help with the accurate assessment of ecological risks of organic pollutants in the presence of NOM. (C) 2016 Elsevier B.V. All rights reserved.