External temperature variations inevitably affect the accuracy of a liquid crystal sensor. Therefore, we propose a novel temperature-compensated fiber volatile organic compound (VOC, using acetone as a model compound) gas sensor. The proposed sensor consists of a short segment of hollow-core fiber (HCF), which is spliced on a multimode fiber. Cholesteric liquid crystal (CLC) is sealed into HCF to sense the temperature, and another type of CLC is coated on the end face of HCF for VOC gas detection. The VOC gas concentration and ambient temperature can be simultaneously measured by monitoring the wavelength shifts of two Bragg reflection peaks caused by two types of CLCs. The effects of the CLC thickness on the sensitivities of temperature and acetone concentration are investigated, and optimal parameters are chosen. An optimal sensor can reach a temperature sensitivity of 2.53 nm/°C and acetone concentration sensitivity of 48.46 nm·L/mmol at 8-44°C. In addition, temperature compensation capability, repeatability, response time, and stability are also researched. The experimental results prove this sensor has great application potential in high-precision real-time VOC gas monitoring and detection.