Copolymers comprising styrene and polyhedral oligomeric silsesquioxane-derived methacrylate (PS-co-PMAPOSS) of various MAPOSS:styrene ratios with Mn over 100 kDa were prepared by concurrent ARGET ATRP RAFT. Fibrous mats of the synthesized copolymers are then fabricated through electrospinning process using various conditions (solvents and POSS content). The results from SEM and EDS analysis unveiled the fibers' physical and chemical characteristics as a clear footprint of the influence of solvent selection (tetrahydrofuran (THF) and dimethylformamide (DMF)). It is evident that liquid liquid phase separation followed by phase segregation of PS and FOSS constitute to the varying degree of porosity in the electrospun fibers. Finally, preliminary tests suggest that highly porous PS-co-PMAPOSS fiber can be modified with high temperature, plasma and silanization for further novel applications. (C) 2014 Elsevier Ltd. All rights reserved.