Magnesium oxide nanoparticles (MgO) were embedded in a cellulose acetate fibrous framework to provide self-decontaminating properties against toxic organophosphates. The concept of a co- continuous polymer blend structure coupled with selective polymer dissolution was used to develop electrospun fibres with novel morphology for application in chemical protective materials. An electrospinning solution built from 60:40 acetonitrile-acetone and 15 wt% of 60 : 40 cellulose acetate- PEO distinct fractions produced fibres that had a degree of continuity of about 0.77 relative to the PEO phase in the cellulose acetate matrix that led to intra- fibre pores with an average diameter of 89 nm, and a surface area of 21.8 m2 g -1. MgO was incorporated into the spinning solution for development of a fibre framework with selfdecontamination properties for toxic organophosphates. In 100 min, the MgO-embedded fibres removed 33% of methyl parathion from a hexane solution while fibres with similar morphology and no MgO removed 14%.