Groundwater contamination by fuel constituents from nonaqueous phase liquids (NAPLs) on top of the groundwater table is a widespread problem. While leaching of classical fuel constituents such as benzene, toluene, ethylbenzene, and xylenes (BTEX) from NAPLs into groundwater has been studied extensively, little is known about the identity and partitioning of polar fuel components. Our work shows that gasoline commonly contains appreciable amounts of aniline, phenol, and their alkyl-substituted homologues as well as a suite of other polar compounds. To assess the potential for leaching of such compounds from NAPLs into groundwater we measured the equilibrium fuel/water partitioning coefficients, K-fw, of some representative constituents in batch systems. K-fw values for the investigated phenols, anilines, benzotriazoles, and S-heterocycles ranged from 0.2 to 1700. These values are up to 3 orders of magnitude lower than the K-fw of benzene. The NAPL-water partitioning of anilines and phenols strongly depends on the compounds' structure as well as on pH and the gasoline composition (e.g., MTBE content). Linear free energy relationships (LFERs) using K-ow or C-w(sat) failed to predict measured K-fw values of polar solutes. In contrast, a polyparameter approach taking into account molecular interactions (van der Waals forces, hydrogen bonds) between solutes and major gasoline components allows precise a-priori predictions of K-fw values of both polar and BTEX fuel constituents without any fit parameters. Since most of the polar fuel constituents studied here are extracted from NAPLs by groundwater much more efficiently than BTEX, such compounds could form contaminant plumes threatening receiving wells before detectable concentrations of BTEX are present.