A thermoelectrically cooled surface-enhanced Raman Spectroscopy (TEC-SERS) fiber optic probe for real-time and in-situ monitoring of volatile organic compounds in gas, liquid, and soil environments. The TEC-SERS probe comprises a sample chamber for receiving a gas sample and a fiber optic Raman probe. The sample chamber comprises an inlet having a semipermeable membrane for separating moisture from the gas sample, a SERS substrate mounted on a thermoelectric cooler, a mass flow device for providing airflow, and an output port. The fiber optic Raman probe is operably coupled to a transparent window in the sample chamber for directing an optical excitation signal to irradiate the SERS substrate and for receiving a SERS optical signal from analytes from the gas sample that are in contact with the SERS substrate.