Pollen’s practically-indestructible shell structure has long inspired the biomimetic design of organic materials. However, there is limited understanding of how the mechanical, chemical, and adhesion properties of pollen are biologically controlled and whether strategies can be devised to manipulate pollen beyond natural performance limits. Here, we report a facile approach to transform pollen grains into soft microgel by remodeling pollen shells. Marked alterations to the pollen substructures led to environmental stimuli responsiveness, which reveal how the interplay of substructure-specific material properties dictates microgel swelling behavior. Our investigation of pollen grains from across the plant kingdom further showed that microgel formation occurs with tested pollen species from eudicot plants. Collectively, our experimental and computational results offer fundamental insights into how tuning pollen structure can cause dramatic alterations to material properties, and inspire future investigation into understanding how the material science of pollen might influence plant reproductive success.