The present work demonstrates the role of organic and inorganic composites in amending the sensing efficiency towards methanol, ethanol and propanol. The hazardous effects of alcohol inhalation, such as blindness, organ failure and other harmful effects, make it indispensable to fabricate suitable sensing devices with higher sensing responses. The higher operating temperatures (>200 °C) of metal oxides act as bottlenecks for their utilisation as gas sensors under ambient conditions. Therefore, adding suitable fillers like Multi-Walled Carbon Nanotubes to metal oxides enhances their sensitivity and selectivity under ambient conditions. For this purpose, metal oxide Titanium dioxide is integrated into a Multi-Walled Carbon Nanotube to form thin film chemical sensors for methanol, ethanol and propanol vapour detection. The Titanium dioxide (TiO2)-Multi-walled carbon nanotube (MWCNT) film has been deposited using a drop-casting method, and the solution of the nanocomposite film has been synthesised using the chemical mixing and dispersion route. The sensing properties of Titanium Dioxide-Multi-Walled Carbon Nanotube (TiO2-MWCNT) films were evaluated through electrical conductivity measurements and compared with optical (UV-visible spectroscopy) and spectroscopic analyses (Fourier Transform Infrared (FTIR) spectroscopy) under ambient conditions. Among the tested alcohol vapours, the TiO2-MWCNT film exhibited the highest sensitivity to methanol (12.29 ppm−1) and the lowest sensitivity to propanol (4.9 ppm−1). The electrical sensing results were in strong agreement with the optical and spectroscopic findings, as methanol exposure led to the most significant deviations in band shifts and peak positions of the sensing film.