Novel composite sub-micron fibers materials, consisting of superfine powdered diatomite (SPD) and fibrous poly (vinyl alcohol) (PVA), were fabricated by electrospinning. SPD was obtained after high energy ball milling for 6h high energy ball milling with 10% (wt%) Polyvinyl pyrrolidone (PVP) as dispersant. The diameters of SPD (400 nm-1000 nm) were 30 times less than that of the normal powdered diatomite particles, and SPD also had pores inside based on Rhodamine B (RhB) micro-pollutant. The composite sub-micron fibers were composed by three dimensional networks from PVA sub-micron fibers, on which SPD particles were randomly attached on. The composite sub-micron fibers exhibited excellent mechanical behavior and stable thermal decomposition property in the temperature from 275 degrees C to 300 degrees C. Comparing with PVA sub-micron fibers, SPD-PVA composite sub-micron fibers possess extra 36% adsorption capacity to RhB, which was due to 48.5% (wt%) of SPD in fibers. Conserving the adsorptive functionality of SPD particles in electrospinning non-woven polymeric fiber, could enable them to be used in the fields of adsorbants.