Stress detection of the conical frustum window is a very important issue to ensure the safety of deep manned submersibles. In this paper, we propose a method based on polarization imaging to evaluate the stress accumulation and recovery in the conical frustum window. An experimental setup of Mueller matrix polarimetry is built, and the samples are made by referring to the typical conical frustum windows in submersibles. By pressurizing different pressures on the samples, we can find the changes of their Mueller matrix images and further derived polarization parameters.  The results show that the polarization parameters can characterize the stress transfer process and the elastic–plastic transformation process of the window under different pressurization pressures. We also use a two-layered wave plate model to simulate the stress distribution in the window, which reveals different performances of the former and latter layers of the window under pressurization. Finally, we use a finite element model to simulate and understand some of the above experimental results. This proposed method is expected to provide new possibilities for monitoring the window stress and further ensure the safety of deep manned submersibles.