Rifapentine crystals with different habits were prepared by recrystallization from selected solvents, such as methanol, ethanol, chloroform, and acetic acid. Scanning electron microscopy, X-ray powder diffractometry, infrared spectrometry, and differential scanning calorimetry were used to investigate the physicochemical characteristics of the prepared crystals. The comparative dissolution behaviors of the newly developed crystals and of rifapentine without being treated were also studied. Results show that the newly developed crystals were different from each other with respect to physical properties but were identical chemically. Needle-shaped crystals were obtained from methanol, ethanol, and chloroform solvents, and the block-shaped crystals were obtained from acetic acid solvent. X-ray diffraction spectra and differential scanning calorimetry investigation on those developed crystals clearly indicate that rifapentine has different crystal structure modification. When the crystal was obtained from acetic acid, the change of crystal habit was originated from the crystal structure modification. The dissolution rate of newly developed crystals was found to be higher than that of rifapentine without being treated. However, the modified crystal obtained from acetic acid shows the lower dissolution rate than crystals obtained from other solvents.