A porous silicon microcavity (PSMC) sensor has been made for vapors of solvent solutions, and a method has been developed in order to obtain simultaneous determination of two volatile substances with different concentrations. In our work, the temperature of the solution and the velocity of the air stream flowing through the solution have been used to control the response of the sensor for ethanol and acetone solutions. We study the dependence of the cavity-resonant wavelength shift on solvent concentration, velocity of the airflow and solution temperature. The wavelength shift depends linearly on concentration and increases with solution temperature and velocity of the airflow. The dependence of the wavelength shift on the solution temperature in the measurement contains properties of the temperature dependence of the solvent vapor pressure, which characterizes each solvent. As a result, the dependence of the wavelength shift on the solution temperature discriminates between solutions of ethanol and acetone with different concentrations. This suggests a possibility for the simultaneous determination of the volatile substances and their concentrations.