Accurate cooling crystallization is vitally important in the production of highly specialized fine chemicals and pharmaceutical engineering, etc. Herein, a novel hollow fiber membrane-assisted cooling crystallization (MACC) was developed to achieve precise nucleation and self-seeding process control. Poly-tetrafluoroethylene (PTFE) and polyethersulfone (PES) membrane with diverse interfacial induced nucleation and thermal conduction properties were introduced to accelerate the nucleation and then transfer the automatically detached crystal seed into the crystallizer. Polymeric membrane can dominate the nucleation kinetic and hinder the secondary nucleation, which was validated from the theoretical model and on-line detective experiments. The crystal product manufactured by MACC possessed better morphology, larger mean size (>1.35 mm), higher purity (>99.5 wt%) and narrower size distribution than the conventional cooling crystallization. Space-time process decoupling between nucleation and crystal growth can be realized via auto-screening uniform nuclei in the membrane modules and controllable growth in the crystallizer during MACC.