AbstractThe double quench phase separation is a simplified type of continuous cooling process that is widely seen in industrial processes for polymeric membrane formation. Uncommon quenching conditions can lead to the creation of novel membrane microstructures. This study aims to theoretically investigate the impact of nonisothermality on the morphology formation during the double‐quench thermally‐induced phase separation process. First, quench is employed during different stages of phase separation to observe the possibility of secondary morphology formation. Next, two initial quench temperatures are selected, one shallow and the other deep. The initial solution temperature and the secondary quench temperature are kept constant to inspect the impact of the initial quench temperature on the structure formation. Lastly, the results of the secondary quench are compared with and without employing the enthalpy of demixing. Results verified that the stage of phase separation, the initial and secondary quench temperatures, cooling rate, and the secondary quench composition are the most important parameters in the the nonisothermal double quench phase separation process. The morphology should be well‐developed in order for the secondary structure formation. In addition, it is shown that heat generation during demixing in the primary and secondary quenches significantly influences the secondary morphology formation.