Polarization crosstalk is a phenomenon that the powers of two orthogonal polarization modes propagating in a polarization maintaining (PM) fiber couple into each other. Because there is certain mathematical relationship between the polarization crosstalk signals and external perturbations such as stress and temperature variations, stress and temperature sensing in PM fiber can be simultaneously achieved by measuring the strengths and locations of polarization crosstalk signals. In this paper, we report what we believe the first distributed temperature sensing demonstration using polarization crosstalk analysis in PM fibers. Firstly, by measuring the spacing changes between two crosstalk peaks at different fiber length locations, we obtained the temperature sensing coefficient (TSC) of approximately −0.73 μm/(°C•m), which means that the spacing between two crosstalk peaks induced at two locations changes by 0.73 μm when the temperature changes by 1 °C over a fiber length of 1 meter. Secondly, in order to bring different temperature values at different axial locations along a PM fiber to verify the distributed temperature sensing, four heating-strips are used to heat different fiber sections of the PM fiber under test, and the temperatures measured by the proposed fiber sensing method according to the obtained TSC are almost consistent with those of heating-strips measured by a thermoelectric thermometer. As a new type of distributed fiber temperature sensing technique, we believe that our method will find broad applications in the near future.