Present study aims to investigate the migration of materials onto the surface of workpiece and electrode during fine-finish die-sinking and milling micro-EDM of tungsten carbide using pure tungsten electrode. The effect of materials transfer on the machined surface characteristics is also presented. The machined surfaces have been examined under scanning electron microscope (SEM) and energy dispersive X-ray (EDX) in order to investigate the changes in chemical composition due to the migration of materials. It has been observed that materials from both workpiece and electrode transfer to each other depending on machining conditions and discharge energy. A significant amount of carbon migrates to both electrode and workpiece surface due to the decomposition of dielectric hydrocarbon during breakdown. The migration occurs more frequently at lower gap voltages during finish die-sinking micro-EDM due to low spark gap and stationary tool electrode. Milling micro-EDM suffers from lower amount of carbon migration and fewer surface defects which improve the overall surface finish and reduce surface roughness significantly.