There are many kinds of materials or methods used to make optical microcavities, and they have many different geometric structures. And electrospinning technique has become a very convenient and easy one to prepare polymer fiber. Based on this situation, PM597-doped polymer solution was prepared into high-performance fibers with different diameters by electrospinning technology in our work. In order to better study the temperature sensing of polymer fiber whispering gallery mode, we have placed it on two different substrates with gold and aluminum. A 532 nm pulsed laser beam was used to excite a single fiber in the radial direction, then the whispering gallery mode (WGM) laser was observed and the distribution of WGM was determined by theoretical calculations. The threshold of samples on aluminum substrate is 0.4 μJ. In addition, it is found that the samples on aluminum substrate performed better in temperature sensing, and the value is 0.13 nm/℃. As a result, WGM polymer fiber microcavities on aluminum substrate made by electrospinning technology have very broad development prospects in biosensing, optical pump lasers and other applications.