Display omitted •Different silk fibroin (SF) porous microstructures have been obtained by tuning solution, regeneration and post-processing•-Physical-chemical properties of the obtained materials depend on processing method.•The suitability of the microstructures for water remediation has been demonstrated. The present work reports on the control of silk fibroin (SF) porous structures performance through various processing methods. The study includes the analysis of two dissolving techniques (CaCl2/H2O/EtOH ternary and LiBr/H2O binary solutions), three regeneration methods (gelation, lyophilization and gas foaming) and one post-processing (EtOH). In all the cases, followed steps lead to SF structures with porosity values above 94% and large surface areas. Also, results about samples microstructure, secondary organization, crystallinity and water behavior, reveal a direct correlation between processing and SF properties. Thanks to the achieved progress, the SF varying porous structures were evaluated for metalloids (As5+ and As3+) and heavy metals (Cr6+ and Cr3+) adsorption, observing a direct relationship between samples processing and ionic species adsorption ability. Thus, it is shown that the control of the properties of SF based porous structures through processing, represents a suitable and ecofriendly approach for the development of bio-based materials for environmental applications.