Alcohol intoxication has a dangerous effect on human health and is often associated with a risk of catastrophic injuries and alcohol-related crimes. A demand to address this problem adheres to the design of new sensor systems for the real-time monitoring of exhaled breath. We introduce a new sensor system based on a porous hydrophilic layer of submicron silica particles (SiO2 SMPs) placed on a one-dimensional photonic crystal made of Ta2O5/SiO2 dielectric layers whose operation relies on detecting changes in the position of surface wave resonance during capillary condensation in pores. To make the active layer of SiO2 SMPs, we examine the influence of electrostatic interactions of media, particles, and the surface of the crystal influenced by buoyancy, gravity force, and Stokes drag force in the frame of the dip-coating preparation method. We evaluate the sensing performance toward biomarkers such as acetone, ammonia, ethanol, and isopropanol and test sensor system capabilities for alcohol intoxication assessment. We have found this sensor to respond to all tested analytes in a broad range of concentrations. By processing the sensor signals by principal component analysis, we selectively determined the analytes. We demonstrated the excellent performance of our device for alcohol intoxication assessment in real-time.