Thermally induced phase separation (TIPS) has been developed to prepare porous membranes. The porous structures are mainly dependent on diluents adopted in the TIPS process. We obtained two typical morphologies of poly(vinylidene fluoride) (PVDF) membranes using cyclohexanone (CO) and propylene carbonate (PC) as diluents, respectively. SEM observation displays that porous spherulites are formed from PVDF/CO system, whereas smooth particles result from PVDF/PC system. The TIPS processes of these two systems have been investigated in detail by optical microscope observation and temperature-dependent FTIR combined with two-dimensional infrared correlation analysis. Rapid crystallization of PVDF can be seen around 110 degrees C in the PVDF/CO system, which is consistent with the results of temperature-dependent FTIR spectra. The spectral evolution indicates a transform of PVDF from amorphous to -phase after 110 degrees C. The s(CO) band at 1712 cm-1 narrows and the s(CF) band at 1188 cm-1 shifts to 1192 cm-1 before crystallization, which implies the destruction of interaction between PVDF and CO. In contrast, the PVDF/PC system shows slow crystallization with all-trans conformation assigned to -phase and -phase below 60 degrees C but no obvious change of polymer-diluent interaction. We propose two mechanisms for the different phase behaviors of PVDF/CO and PVDF/PC systems: a solid-liquid phase separation after destruction of polymer-diluent interaction in the former, and a liquid-liquid phase separation process coupled with rich-phase crystallization in the later. This work may provide new insight into the relationship among morphologies, crystal forms, and phase separation processes, which will be helpful to adjust membrane structure. (c) 2013 Wiley Periodicals, Inc.