A study of the phase transitions in ZIF-7 (zeolitic imidazolate frameworks- (Zn(PhIm)2, PhIm = benzimidazolate)) as a function of guest occupancy and temperature was reported. Raman spectra of an as-synthesized sample were collected in air between 297 and 421 K. The major contributions of the spectra come from the vibrational modes of the benzimidazolate ligand. Upon heating, most of the Raman bands remain similar and keep the same frequencies until 357 K, indicating that the structure of ZIF-7 seems to be stable in this temperature range. Above 357 K, strong modifications are observed in the regions corresponding to the lattice modes. The formation of ZIF-7-II is attributed to the loss of dimethylformamide (DMF) solvent molecules from the ZIF-7-I framework. This can be confirmed by the differential scanning calorimetry and thermogravimetric analysis traces of ZIF-7-I. The highly-distorted and locally-strained nature of ZIF-7-II leads to its poor crystallinity, reflected by X-ray powder diffraction and scanning electron microscope.