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We report on a highly sensitive measurement of the relative humidity of air, which utilizes a guided-mode resonance (GMR) of a multilayer dielectric structure (MDS) and the spectral interference of s- and p-polarized waves reflected from the MDS. We employ the MDS represented by four bilayers of TiO2/SiO2 with a termination layer of TiO2 and demonstrate that the GMR shows up as a shallow and asymmetric dip. The GMR enables us to measure the relative humidity (RH) of air with sensitivities of 0.031-0.114 nm/%RH. In addition, by employing