The distribution of 1,10-phenanthroline (phen) in micellar solutions of the nonionic surfactants Triton X and C12En with varying poly (ethylene oxide) chain lengths has been studied by potentiometry, calorimetry, and fluorometry at 298 K. Micelles accommodate 1,10-phenanthroline according to the reaction, phen + Y-m = Y-m(phen), where Ym denotes a surfactant molecule aggregated in micelles. The constant Km for the reaction of Triton X increases as a linear function of n*, the number of ethylene oxide (EO) groups, as K-m = K(EO)n* + K-c. Nonzero K-EO and K-c values suggest a heterogeneous inner structure of the micelle, i.e., the hydrophobic core surrounded by a hydrophilic poly (ethylene oxide) (PEO) shell. On the basis of molar volumes, the intrinsic thermodynamic parameters of transfer of 1,10-phenantholine were extracted. The enthalpy and entropy of transfer of 1,10-phenanthroline from the PEO shell to the core are found to be small and negative. By using KEO and Kc values for C12En obtained by fluorometry, individual fluorescence spectra of 1,10-phenanthroline in the PEO shell and core were extracted. The fluorescence intensity of 1,10-phenathroline accommodated in the core, like in organic solvents, is significantly reduced relative to that in water. These facts indicate that the aromatic rings of 1,10-phenanthroline penetrate into the hydrophobic core, while its hydrophilic N site is still hydrated in the PEO shell.