A doubly cladding single-mode fiber humidity sensor is fabricated by agarose. The sensor has an insertion loss of -0.08 dB and a power change of -17.83 dB. The responses of the sensor to a relative humidity (RH) range form 30% to 100% at a temperature range form 25 to 34 oC are validated. The experiments demonstrate that the absorbability of agarose gel to moisture decreases with increasing RH in measured gas. We propose a calibration method that uses lookup tables and construct a corresponding calibration matrix. Using the sensor, we conduct real-time monitoring of RH in fresh concrete during its hardening process.