Currently there is a growing interest in developing novel bioproducts and biomaterials derived from renewable sources that can reduce the dependence on fossil fuel feedstock. In this study a protein concentrate from microalgae Botryococcus braunii residual biomass (MPC) from a biorefinery process was used as a biopolymer to develop ultrafine fibers by electrospinning. Experiments were designed to study the effect of different formulations of MPC, poly(ethylene oxide) and pH on morphology and diameter of fibers. The results indicated MPC fibers from acidic solutions prepared at pH 1 had smoother and smaller diameter than those fibers from alkaline solutions (pH 12). Moreover, under the conditions studied, it was conclude that pH and the concentration of MPC were the most significant factors in determining the diameter and morphology of the fibers obtained. Fourier transform infrared analysis showed there is a slight frequency shift for the secondary structure of MPC as induced by change in pH of the polymer solutions. Likely this change in the protein structure improved the physical chain entanglement in the polymer blend. The results of this work revealed a potential to develop fibers from MPC from residual biomass by a promising technique that may find many end-use applications.