In this research, series of PVDF microporous films with various polymer concentrations and thickness were prepared through thermally‐induced phase separation in air condition with diphenyl carbonate as the diluent. Effects of polymer concentration and film thickness on the formation kinetics of microporous structure of PVDF thin films were in situ investigated via TII technique. The instantaneous heat conduction inside the films during film formation was also evaluated. Two types of parameter models were adopted in order to disclose the time and location dependence of TIPS film solidification kinetics, respectively. Hierarchical microstructures, crystallization behavior and thermal properties of the TIPS films were also characterized by SEM, DSC, and TGA, respectively. The current study could supply an insight into the fabrication of PVDF microporous films with target microstructure and desirable performance.