Coal-tar-based sealcoat, used extensively on parking lots and driveways in North America, is a potent source of PAHs. We investigated how concentrations and assemblages of PAHs and azaarenes in runoff from pavement newly sealed with coal-tar-based (CT) or asphalt-based (AS) sealcoat changed over time. Samples of simulated runoff were collected from pavement 5 h to 111 d following application of AS or CT sealcoat. Concentrations of the sum of 16 PAHs (median concentrations of 328 and 35 μg/L for CT and AS runoff, respectively) in runoff varied relatively little, but rapid decreases in concentrations of azaarenes and low molecular weight PAHs were offset by increases in high molecular weight PAHs. The results demonstrate that runoff from CT-sealcoated pavement, in particular, continues to contain elevated concentrations of PAHs long after a 24-h curing time, with implications for the fate, transport, and ecotoxicological effects of contaminants in runoff from CT-sealcoated pavement.