The solvent-free, seed-directed synthesis using natural precursors has emerged as a sustainable route for the synthesis of zeolite. Albeit the significant progress in the synthesis techniques, the crystallization behaviors of zeolites are somewhat elusive. Herein, we performed a detailed investigation of the crystallization behaviors of ZSM-5 zeolites synthesized through the solvent-free, seed-directed route using rice husk silica as starting materials. The crystallization at 180 °C is completed rapidly in 10 h, with an ultrahigh zeolite yield of at least 95%. Moreover, we evaluated the crystallization kinetics at different temperatures using the nonlinear Avrami equation and found instantaneous nucleation with three-dimensional growth in the studied temperature range, with activation energies for nucleation, transition, and crystal growth of 137, 51, and 51 kJ mol-1, respectively, indicating that nucleation is the rate-determining step. Further investigation of the structural and morphological evolution revealed a preference for secondary nucleation over the seed-growth mechanism. Crystallization proceeds via structural rearrangement within the solid system. We anticipate that our work will provide extensive insights that increase the understanding of zeolite crystallization and expand the highly sustainable production of zeolites.