A single-mode polymer optical fiber (POF) with highly photosensitive core doped with benzil dimethyl ketal (BDK) is fabricated and used for writing Bragg grating through the two-beam interference method. The Bragg wavelength of the grating is about 1570 nm, while the full-width at half-maximum (FWHM) of the reflection peak is 0.3 nm. The temperature response of POF Bragg grating is theoretically analyzed and experimentally measured in contrast to silica optical fiber Bragg grating (FBG). The result shows that the temperature character of POF Bragg grating is negative, which is opposite to the silica optical FBG. The absolute value of the temperature response of POF Bragg grating is one order of magnitude higher than that of the silica optical FBG, making POF Bragg grating appear to be very attractive for constructing temperature sensors with high resolution.