The systems {methylpiperidine-water} show partial miscibility that depends on the nature of the amine isomer. A thermodynamic analysis of these systems requires knowledge of excess properties of methylpiperidine isomers with water. Excess molar enthalpies were measured at pressure 0.5 MPa and temperatures from (303.15 to 338.15) K and from (308.15 to 328.15) K for 2-methylpiperidine and N-methylpiperidine, respectively. Specific heat capacities of pure and aqueous solutions of both methylpiperidine isomers were determined at 0.1 MPa and temperatures from (283.15 to 333.15) K.