A microstructured polymer optical fiber (mPOF) Bragg grating sensor system for the simultaneous measurement of temperature and relative humidity (RH) has been developed and characterized. The sensing head is based on two in-line fiber Bragg gratings recorded in a mPOF. The sensor system has a root mean square deviation of 1.04 % RH and 0.8 °C in the range 10 to 90% RH and 20 to 80 °C. The proposed sensor system is easy to fabricate, cheap and compact.