Solubility of two isomers of cyanopyridine (CNP) in various solvents were determined by the gravimetric method in the temperature range from 268.15 K to 318.15 K at atmospheric pressure. The experimental results show that the solubility of 3-cyanopyridine increased dramatically over 298.15 K, whereas 4-cyanopyridine was more stable at the same state. The modified Apelblat model, polynomial equation, the Buchowski-Ksiazczak lambda h equation, and Wilson model were employed to correlate the experimental data. The Wilson model provides better agreement than the other models in terms of the 3- and 4-cyanopyridine. Moreover, molecular simulation was also used to present the interaction between 3-CNP, 4-CNP, and the solvent molecules, which can give an explanation for the solubility behavior in solvents.