The present work discusses and compares the toluene sensing behavior of polyaniline (PANI) and graphene/polyaniline nanocomposite (C-PANI) films. The graphene-PANI ratio in the nanocomposite polymer film is optimized at 1:2. For this, N-methyl-2-pyrrolidone (NMP) solvent is used to prepare PANI-NMP solution as well as graphene-PANI-NMP solution. The films are later annealed at 230 °C, characterized using scanning electron microscopy (SEM) as well Fourier transform infrared spectroscopy (FTIR) and tested for their sensing behavior towards toluene. The sensing behaviors of the films are analyzed at different temperatures (30, 50 and 100 °C) for 100 ppm toluene in air. The nanocomposite C-PANI films have exhibited better overall toluene sensing behavior in terms of sensor response, response and recovery time as well as repeatability. Although the sensor response of PANI (12.6 at 30 °C, 38.4 at 100 °C) is comparatively higher than that of C-PANI (8.4 at 30 °C, 35.5 at 100 °C), response and recovery time of PANI and C-PANI varies with operating temperature. C-PANI at 50 °C seems to have better toluene sensing behavior in terms of response time and recovery time.