Spectrofluorometric probe methods are developed and examined regarding their ability to model preferential solvation around probe molecules in binary solvents. The first method assumes that each fluorophore is solvated by only one type of solvent molecule and that each fluorophore contributes to the emission intensity. Expressions for this model are illustrated using fluorescence behavior of pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene dissolved in binary n-heptane + 1,4-dioxane and n-heptane + tetrahydrofuran mixtures. The second method treats the solvational sphere as a binary solvent microsphere, with the fluorophore's energy in both the ground and the excited states mathematically expressed using the "nearly ideal binary solvent" (NIBS) model. Expressions derived from this model are illustrated using fluorescence behavior of 9,9'-bianthracene and 9,9*-bianthracene-10-carboxaldehyde in binary toluene + acetonitrile and dibutyl ether + acetonitrile.