The gel-crystal transition during crystallization of cefpiramide was systematically investigated for the first time in this work. The results show that gelation is a metastable state, derived from the three-dimensional mesh self-assembly structure made by carbonyl, amide, and carboxy groups through hydrogen-bonding interactions. After that, the gelator slowly assembles to the crystals, the equilibrium of gelation is disrupted, and the gel finally reverts to the crystal.