Electrospinning has attracted great attention in recent years from different industries including biomedical engineering. Owing to the relative ease of fabricating ultrafine fibres with core-shell structures, emulsion electrospinning has been investigated intensively for making nanofibrous delivery vehicles for local and sustained release of bioactive or therapeutic substances, especially biomolecules such as growth factors. In preparing emulsions for electrospinning, different surfactants, ionic or non-ionic, can be used, which may subsequently influence the evolution of the core-shell structure in the electrospun emulsion jet or fibre. In this investigation, emulsions consisting of deionized water or phosphate buffer saline as the water phase, a poly(lactic-co-glycolic acid) solution as the oil phase and Span 80 (a non-ionic surfactant) or sodium dodecyl sulfate (an ionic surfactant) were electrospun into fibres for studying the core-shell structure and its evolution in emulsion electrospun fibres. Different microscopies were employed to study the morphological changes of the water phase in fibre samples collected at different locations along the jet (or fibre) trajectory during emulsion electrospinning. It was found that the evolution of the fibre core-shell structure was significantly different when different surfactants were used. If Span 80 was the surfactant, the water phase within the thick emulsion jet (or fibre) close to the Taylor cone existed in a discrete state whereas in ultrafine fibres collected beyond a certain distance from the Taylor cone, a mostly continuous water-phase core was observed. If sodium dodecyl sulfate was the surfactant, the core-shell structure in the thick jet (or fibre) was irregular but relatively continuous. A single core core-shell structure was eventually developed in ultrafine fibres. The core-shell structure in electrospun fibres and its evolution were also affected by the emulsion composition (e.g. polymer solution concentration, water-phase volume, and ion addition in the water phase).