We studied the dependence of the Brillouin frequency shift (BFS) on the water-absorption ratio in poly(methyl methacrylate)-based polymer optical fibers (POFs) to clarify the effect of the humidity on POF-based Brillouin sensors. The BFS, deduced indirectly using an ultrasonic pulse-echo technique, decreased monotonically as the water absorption ratio increased, mainly because of the decrease in the Young's modulus. For the same water absorption ratio, the BFS change was larger at a higher temperature. The maximal BFS changes (absolute values) at 40, 60, and 80 °C were 158, 285, and 510 MHz, respectively (corresponding to the temperature changes of ∼9 °C, ∼16 °C, and ∼30 °C). Thus, some countermeasure against the humidity is indispensable in implementing strain/temperature sensors based on Brillouin scattering in POFs, especially at a higher temperature. On the other hand, Brillouin-based distributed humidity sensors might be developed by exploiting the BFS dependence on water absorption in POFs.