Incorporating activated bentonite clay (BC) into electrospun nanofibres is an established strategy for modulating adsorption behaviour. In the present study, naturally occurring calcium BC was completely activated to sodium BC with a 4 wt% sodium carbonate (Na2CO3)/BC ratio. Composite nanofibre webs were produced from cellulose acetate (CA)/BC spinning solutions using free surface electrospinning, and the effect of BC loadings on viscosity, surface tension and electrical conductivity prior to spinning was studied. Chemical and thermal analyses were conducted on as-spun fibres, and SEM and TEM revealed a nanofibrous morphology consisting of an interpenetrating network of fibres and semi-spherical features resembling jellyfish with an internal core of BC.