Biomaterials are challenging, yet vastly promising templates for engineering unusual inorganic materials with unprecedented surface and structural properties. In the current work, a novel biotemplate-based photocatalytic material was synthesized in the form of corrugated TiO2 microspheres by utilizing a sol-gel methodology where Ambrosia trifida (Ab, Giant ragweed) pollen was exploited as the initial biological support surface. Hierarchically synthesized TiO2 microspheres were structurally characterized in detail via SEM-EDX, Raman spectroscopy, XRD and BET techniques in order to shed light on the surface chemistry, crystal structure, chemical composition and morphology of these novel material architectures. Photocatalytic functionality of the synthesized materials was demonstrated both in gas phase as well as in liquid phase. Along these lines, air and water purification capabilities of the synthesized TiO2 microspheres were established by performing photocatalytic oxidative NOx(g) storage and Rhodamine B(aq) degradation experiments; respectively. The synthetic approach presented herein offers new opportunities to design and create sophisticated functional materials that can be used in micro reactor systems, adsorbents, drug delivery systems, catalytic processes, and sensor technologies.