Three quinoxaline derivatives are investigated both experimentally and theoretically to assess their ability for the methanol oxidation and harvesting of hydrogen. In inert solvents, the nonplanar compounds exhibit very weak fluorescence from the lowest excited singlet state, whereas the planar and rigid chromophore emits non-Kasha fluorescence from the S2(ππ*) state despite the proximity of the S1(nπ*) state. In methanol, hydrogen-bonded complexes with solvent molecules are formed, and in all chromophores, the lowest singlet state is populated after excitation of the S2(ππ*) state. The switch from non-Kasha emission of the planar compound in inert solvents to regular emission in methanol is related to reduced symmetry of the hydrogen-bonded complex with methanol which results in effective mixing of ππ* and nπ* states and fast internal conversion to the lowest excited singlet state. The S1(nπ*) state of the hydrogen-bonded complex has charge-transfer character, and for all compounds in methanol, hydrogen transfer to the chromophore is observed. The chromophores retain the transferred hydrogen atoms, serving both as photocatalysts and as hydrogen storage materials. Undesired dark side reactions that occur are also discussed.