This paper presents, for the first time to the best of our knowledge, simultaneous temperature and relative humidity (RH) measurement using a machine learning (ML) model in Rayleigh-based Optical Frequency Domain Reflectometry (OFDR). The sensor unit consists of two segments: bare and polyimide-coated fibers, each with different sensitivities to temperature. The polyimide-coated fiber is RH-sensitive, unlike the bare fiber. We propose the ML approach to avoid manual post-processing data and maintain relatively high accuracy of the sensor. The root mean square error (RMSE) values for the 3 cm length of the sensor unit were 0.36 °C and 1.73% RH for temperature and RH, respectively. Furthermore, we investigated the impact of sensor unit lengths and number of data points on RMSE values. This approach eliminates the need for manual data processing, reduces analysis time, and enables accurate, simultaneous measurement of temperature and RH in Rayleigh-based OFDR.