Polymer optical fibre Bragg grating (POFBG) sensors are of high interest due to their enhanced fracture toughness, flexibility in bending, and sensitivity in stress and pressure monitoring applications compared to silica-based sensors. The POFBG sensors can also detect humidity due to the hydrophilic nature of some polymers. However, multi-parameter sensing can cause cross-sensitivity issues in certain applications if the temperature and humidity measurements are not adequately compensated. In this work, we demonstrate the possibility of selectively tuning sensors’ temperature and humidity sensitivities to the desired level by applying a certain amount of fibre pre-strain. The temperature sensitivity of POFBG sensors fabricated in perfluoropolymers (CYTOP) can be selectively tuned from positive to negative values, having the option for insensitivity in specific temperature ranges depending on the amount of the applied pre-strain. The humidity sensitivity of sensors can also be changed from positive values to insensitivity. The importance of thermal annealing treatment of POFBG sensors for improved repeatability in temperature measurements is also reported. An array of 4 multiplexed POFBGs was fabricated, and each sensor was pre-strained accordingly to demonstrate the possibility of having targeted temperature and humidity sensitivities along the same fibre.