This experimental and theoretical study is devoted to the investigation of head-on collisions of two drops of immiscible liquids. In the experiments, pairs of drops are made to collide at well-defined kinetic and geometric conditions. The sizes and relative velocity of the colliding drops close to the point of impact are measured by means of image processing. The deformed states after the impact, their evolution with time, and their stability are studied by visualization. The theory considers the dynamics of the rim formed at the edge of a radially spreading lamella due to capillary forces at the free surfaces of the lamella and at the liquid/liquid interface. The equations of the rim formation and motion are obtained from the volume, mass and momentum balance equations which account for the inertial, viscous and capillary effects. The theory predicts the evolution of the main geometrical parameters of the liquid mass formed by the drop collision: thickness of the lamella, diameter, and size of the rim cross-section. The theoretical predictions agree well with the experimental data, although no adjustable parameters are used in the model.