The development of easier, cheaper, and more effective synthetic strategies for hierarchical multimodal porous materials and multi-shell hollow spheres remains a challenging topic to utilize them as adsorbents in environmental applications. Here, the hierarchical architecture of multi-shell hollow micro-meso-macroporous silica with pollen-like morphology (MS-HMS-PL) has been successfully synthesized via a facile soft-templating approach and characterized for the first time. MS-HMS-PL sub-microspheres showed a trimodal hierarchical pore architecture with a high surface area of 414.5 m2 g-1, surpassing most of the previously reported multishelled hollow nanomaterials. Due to its facile preparation route and good physicochemical properties, MS-HMS-PL could be a potential candidate material in water purification, catalysis, and drug delivery. To investigate the applicability of MS-HMS-PL as an adsorbent, its adsorption performance for Cr(VI) in water was evaluated. Important adsorption factors affecting the adsorption capacity of adsorbent were systematically studied and Kinetics, isotherms, and thermodynamics parameters were computed via the non-linear fitting technique. The maximum capacity of adsorption computed from the Langmuir isotherm equation for Cr(VI) on MS-HMS-PL was 257.67 mg g-1 at 293 K and optimum conditions (pH 4.0, adsorbent dosage 5.0 mg, and contact time 90 min).