A droplet-type optical fiber volatile organic compound (VOC) sensor based on polydimethylsiloxane (PDMS) is proposed to detect the leakage of VOCs. The droplet-type sensor is formed from a standard single-mode optical fiber that is bent and encapsulated in PDMS. In the experiment, the concentration of the VOC is obtained by monitoring the wavelength drift of output spectrum of the sensor. The experimental results show that when PDMS absorbs the VOC, its volume expands, and the effective bending length of the droplet-type optical fiber structure decreases. The output spectrum of the sensor is blue-shifted when the volume fraction of the VOC ranges from 0 to 9960×10-6. The sensitivity and detection accuracy of the sensor are -0.542 pm/10-6 and 37×10-6, respectively, with a response time of 8.3 min. When the intensity demodulation method is adopted, the sensitivity of the sensor is the highest (-3.22×10^-4 dB/10-6) at the wavelength of 1539.00 nm, and its detection accuracy is 31×10-6.