The expansion of vermiculite using microwave irradiation is an environmentally friendly and efficient method that can enhance the material’s adsorption performance. This study investigated the microwave irradiation of vermiculite with five different particle sizes (4/2/1/0.5/0.2 mm) and found that the adsorption capacity for Pb²⁺ increased with larger particle sizes. The equilibrium adsorption capacity reached 15.98 mg/g at 4 mm, representing a 45.01% improvement compared to 0.2 mm. The pseudo-second-order kinetic model effectively described the adsorption kinetics. No significant differences were observed in the specific surface area and pore size distribution of all samples. Thermogravimetric quantitative analysis revealed that larger particle sizes retained interlayer water more effectively. As the particle size decreased, the interlayer water content generally showed a decreasing trend. Fourier-transform infrared spectroscopy analysis also indicated that the -OH groups in larger particle sizes exhibited higher stability. The results suggest that the high content and stability of -OH groups may be key factors in the enhanced adsorption performance for Pb²⁺. This provides new insights for the preparation of environmentally friendly adsorbent materials rich in hydroxyl groups.