The small amplitude oscillatory shear (SAOS) rheological properties of complex coacervate of milk proteins with high (HMC), medium (MMC), and low (LMC) molecular weight chitosan in the optimal ratios of milk proteins to chitosan (15:1, 10:1, and 5:1, respectively) were measured. In addition, the morphological (SEM), structural (XRD), and thermal (DSC) properties of the complex coacervates were investigated in comparison with the milk protein concentrate. Complex coacervates showed the shear-thinning behavior due to a linear decrease of complex viscosity with increasing frequency. Furthermore, the highest complex modulus and the more compact structure under optimal conditions, in terms of the ratio of protein to chitosan and pH, revealed strong electrostatic bonding between proteins and chitosan. All coacervates showed a G′ > G″ (Tanδ<1), indicating the formation of an interconnected gel-like structure that was described by the power law model. The maximum fracture stress was obtained at optimum conditions (R = 15:1, pH =6.7 for HMC; R = 10:1, pH =5.5 for MMC and R = 5:1, pH =4.6 for LMC), indicating the highest intermolecular interaction between milk proteins and chitosan. The coacervates had a completely amorphous structure similar to MPC, and according to DSC results, the ionic bonds between milk proteins and chitosan were not destroyed up to 300 °C. Coacervation leads to purified milk proteins at a low cost. In addition, the coacervates can be used for the encapsulation of heat-sensitive compounds, and also as a stabilizer to improve the texture of food.