The rise of gas-sensing applications and markets has led to microwave sensors associated to polymer-based sensitive materials gaining a lot of attention, as they offer the possibility to target a large variety of gases (as polymers can be easily functionalised) at ultra-low power and wirelessly (which is a major concern in the Internet of Things). A two-channel microstrip sensor with one resonator coated with 1,2 epoxybutane-functionalised poly(ethyleneimine) (EB-PEI) and the other left bare was designed and fabricated for humidity sensing. The sensor, characterised under controlled laboratory conditions, showed exponential response to RH between 0 and 100%, which is approximated to −1.88 MHz/RH% (−0.03 dB/RH%) and −8.24 MHz/RH% (−0.171 dB/RH%) in the RH ranges of 30–80% and 80–100%, respectively. This is the first reported use of EB-PEI for humidity sensing, and performances, especially at high humidity level (RH > 80%), as compared with transducer working frequencies, are better than the state of the art. When further tested in real outdoor conditions, the sensor shows satisfying performances, with 4.2 %RH mean absolute error. Most importantly, we demonstrate that the sensor is selective to relative humidity alone, irrespective of the other environmental variables acquired during the campaign (O3, NO, NO2, CO, CO2, and Temperature). The sensitivities obtained outdoors in the ranges of 50–70% and 70–100% RH (−0.61 MHz/%RH and −3.68 MHz/%RH, respectively) were close to lab results (−0.95 MHz/%RH and −3.51 MHz/%RH, respectively).