A simple deep-ultraviolet (UV) absorption spectrophotometer based on ultraviolet light-emitting diode (UV LED) was developed for the detection of air-borne toluene with a good sensitivity. A fiber-coupled deep UV-LED was employed as a light source, and a spectrometer was used as a detector with a gas cell in between. 3D printed opto-fluidics connectors were designed to integrate the gas flow with UV light. Two types of hollow core waveguides (HCW) were tested as gas cells: a glass capillary tube with aluminum-coated inner walls and an aluminum capillary tube. The setup was tested for different toluene concentrations (10–100 ppm), and a linear relationship was observed with sensitivities of 0.20 mA·U/ppm and 0.32 mA·U/ppm for the glass and aluminum HCWs, respectively. The corresponding limits of detection were found to be 8.1 ppm and 12.4 ppm, respectively.