Producing uniform nanofibers in high quality by electrospinning remains a huge challenge, especially using low concentrated polymer solutions. However, emulsion electrospinning assists to produce nanofibers from less concentrated polymer solutions compared to the traditional electrospinning process. The influence of individual surfactants towards the morphology of the emulsion electrospun poly (ɛ-caprolactone)/bovine serum albumin (PCL/BSA) nanofibers were investigated by using (i) non-ionic surfactant sorbitane monooleate (Span80); (ii) anionic sodium dodecyl sulfate (SDS); and (iii) cationic benzyltriethylammonium chloride, and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer Pluronic F108 of different concentrations. The morphology, along with the chemical and mechanical properties of the fibers, was evaluated by field emission scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, differential scanning calorimetry, water contact angle, and tensile tester. With the addition of surfactants, the electrospinnability of dilute PCL solution was enhanced, with either branched or uniform fibers were obtained. Electrospinning of an emulsion containing 0.4% (w/v) SDS produced the smallest and the most uniform nanofibers (167 ± 39 nm), which was attributed to the high conductivity of the solution. Analysis revealed that the emulsion electrospun nanofibers containing different surfactants and surfactant concentrations differ in fiber morphology and mechanical properties. Results suggest that surfactants have the ability to modulate the fiber morphology via electrostatic and hydrogen bonding, depending on their chemical structure.