The increasing awareness of the harsh environmental and health risks associated with air pollution has placed volatile organic compounds (VOCs) sensor technologies in elevated demand. While the currently available VOC-monitoring technologies are either bulky and expensive, or only capable of measuring a total VOC concentration, the selective detection of VOCs in the gas-phase remains a challenge. To overcome this, a novel method and device based on mid-IR evanescent-wave fiber-optic spectroscopy, which enables enhanced detection of VOCs, is hereby proposed. This is achieved by increasing the number of analyte molecules in the proximity of the evanescent field via capillary condensation inside nano-porous microparticles coated on the fiber surface. The nano-porous structure of the coating allows the VOC analytes to rapidly diffuse into the pores and become concentrated at the surface of the fiber, thereby allowing the utilization of highly sensitive evanescent-wave spectroscopy. To ascertain the effectiveness and performance of the sensor, different VOCs are measured, and the enhanced sensitivity is analyzed using a custom-built gas cell. According to the results presented here, our VOC sensor shows a significantly increased sensitivity compared to that of an uncoated fiber.