This experimental and theoretical study is devoted to the investigation of head-on collisions of two immiscible Newtonian and non-Newtonian droplets. The density of the two droplets is similar, and the viscosity of 0.3% carboxymethyl cellulose droplet is slightly larger than 10 cSt silicone oil. The sizes and relative velocity of the colliding droplets close to the point of impact are measured by means of image processing. The deformed states after the impact and their evolution with time are studied by experimental visualization and the energy evolution with time are discussed by numerical results. The accuracy of the two-dimensional axisymmetric three-phase flow computational model is validated. We study the effects of collisions of non-Newtonian droplets with Newtonian droplets and the subsequent retraction kinetics. Droplet “cannibalization” is commonly observed: after collision and spreading, the droplet retracts rapidly, resulting in a Newtonian droplet wrapping around a non-Newtonian droplet. We show the whole process of droplet collision captured by a high-speed camera and obtain the cloud and velocity vector maps of the droplets by numerical simulation. The droplet wrapping phenomenon is produced by different three-phase interfacial tensions and viscosities. We delineate the different phases of the collision process and discuss the dominant forces in each phase. We calculate the energy evolution of the spreading phase and use it to derive a predictive model for the dimensionless maximum spreading diameter and spreading time.