A process for the treatment of water/oil (W/O) emulsions is described which includes the addition of an ionic liquid, under heating, to a water/oil emulsion containing between 0.5% and 85% of water per volume as a dispersion phase, until the concentration of the ionic liquid in the emulsion remains within the range of 0.01 μL/g to 100 μL/g. The ionic liquid used is a salt of a general C+ A− formula in a liquid state at temperatures below 150° C., where A− is an anion and C+ is a cation, which has at least a hydrophobic alkyl chain connected to a cation group. The heating method includes conventional heating and heating via microwaves. In the heating via microwaves, the salts of the general C+ A− formula present synergic behavior in separation efficiency in relation to conventional heating.