This paper presents novel preparation methods of polyimide and coupling agent,coated on the fibre Bragg grating sensor for monitoring relative humidity.The sensing mechanism that the volume change of the moisture-sensitive polyimide induces the shift of the Bragg wavelength of FBG is used in the RH sensor.The performance of the polymer-coated RH sensor was evaluated under laboratory conditions of temperature over a range of values(20.0-80.0℃)and humidity over a range of RH values(25.0-95.0%).The time response and RH sensitivity of the sensor based on novel polyimide and coupling agent was improved,compared to the previous.A new packaged RH sensor was designed,which was used in detecting the moisture diffusion and evolutions inside of sample made of model simulation materials which exposed to a controlled environment in the lab after casting.Relative humidity inside of sample with time was 100%in the first phase of vapor-saturated,slowly reduced in the latter phase.The results indicate the RH sensor developed provides a feasible method to detect the influence of environment on moisture inside the material in the drying process.