One dimensional MgO nanofibres with high photocatalytic activity were fabricated using the electrospinning method via a polyvinyl alcohol (PVA)/magnesium precursor based system and the dye degradation efficacy of MgO nanofibres was compared with MgO nanospheres. Optimum electrospinning parameters including suitable magnesium precursors were investigated and the formation of MgO nanofibres were confirmed with scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) mapping. Furthermore, the crystalline lattice structure and surface roughness of fabricated nanofibres were evaluated using transmission electron microscopic electron diffraction mode (TEM-SAED) and atomic force microscopy (AFM), respectively. Fabricated MgO nanofibres exhibited excellent photocatalytic degradation activity against widely used model reactive dye, Reactive Yellow (RY). In contrast to MgO nanospheres, electrospun MgO nanofibres completely degraded the reactive dye under UV irradiation. These photocatalytic MgO nanofibres show a great potential to be used in efficient treatment of industrial dye effluents.