A theoretical heat and mass transfer model of volatile liquid lens evaporation on the surface of an immiscible liquid substrate is established in toroidal coordinates. According to the coupled boundary conditions of heat and mass transfer at the lens surface as well as the interfacial cooling effect, the analytical solutions of the temperature field inside the lens and the vapor concentration field around the lens are derived for the first time. Compared with the isothermal model, the change of contact radius calculated by the present model agrees well with the experimental data, especially when the liquid substrate reaches a relatively high temperature. It also reveals that the temperature distribution inside the lens is not uniform, which is similar to the sessile droplet evaporation on a solid substrate surface. In addition, the excess temperature, heat flux, and evaporation flux of the lens–air interface increase monotonically from the lens center to the contact line. Finally, the influences of density ratio and evaporative cooling number E0 on lens mass evaporation rate are analyzed, which shows that the lens mass evaporation rate decreases with increasing density ratio and evaporative cooling number.