The central binary collision of two unequal sized droplets is numerically investigated using the volume of fluid (V.O.F.) methodology. The numerical method based on the solution of the continuity and momentum equations in axi-symmetric formulation is coupled with a recently developed adaptive local grid refinement technique, thus allowing an accurate representation of the interface between the liquid and gas phase. Mass transfer mechanisms are reproduced by solving a transport equation for a colour function representing the mass of one of the colliding droplets before and after collision and mixing. The investigation is performed assuming either constant relative velocity of the colliding droplets or constant total energy of the system, thus creating a combination of the standard non-dimensional parameters affecting the collision process, i.e. Weber (We) and Ohnesorge (Oh) numbers as also droplet diameter ratio (Δ). The reliability of the procedure is first established by comparing predictions with available experimental data. The effect of the above mentioned parameters on ligament’s formation, maximum deformation of the two droplets, the penetration of one droplet into the other and satellite droplet formation is quantified.