The properties of a material change remarkably as a result of the scaling dimensions. The Langmuir-Blodgett (LB) film deposition technique is known to offer precise control over the film thickness and the interparticle separation. To form a well-ordered LB film, it is essential to form a stable Langmuir film at the air-water interface. Here, we report our studies on ultrathin films of TiO2 nanoparticles at air-water and air-solid interfaces. The Langmuir film of TiO2 nanoparticles at the air-water interface was found to be very stable, and it exhibits loose-packing and close-packing phases. The LB films were transferred onto solid substrates for characterization and application. The surface morphology of the LB film was obtained by a field emission scanning electron microscope. The optical and electronic properties of the LB films of TiO2 nanoparticles were studied using UV-vis spectroscopy and current-voltage measurements, respectively. The LB film of TiO2 nanoparticles was employed for ethanol gas sensing, and the sensing performance was compared to that of bulk material. Because of the enormous gain in the surface to volume ratio and the increase in crystalline defect density in the ultrathin LB film of TiO2 nanoparticles, the LB film is found to be a potential functional layer for ethanol sensing as compared to the bulk material.