Cement emulsified asphalt composite binder (CEACB) plays a determining role in the construction of cold recycled asphalt pavements. Understanding the interaction behaviors of cement-emulsified asphalt is very essential to promote the serviceability of CEACB. The objective of this study was to explore the interaction behaviors and mechanism of cement-emulsified asphalt associated with microstructural characteristics and to assess the interaction ability of cement-emulsified asphalt by performing macro-rheological measurements. Firstly, the physico-chemical interaction of cement-emulsified asphalt was qualitatively discussed by analyzing the difference of characteristic peaks based on Fourier transform infrared (FTIR) spectrometer. Secondly, the micro-morphological evolution behaviors of CEACB attributing to the cement-emulsified asphalt interaction were investigated by using a fluorescence microscope (FM) and laser particle size analyzer (LPSA). Thirdly, the microstructural characteristics of CEACB were studied by observing the spatial network structure through the scanning electron microscopy (SEM). Finally, the macro-rheological index based on dynamic rheological shear (DSR) test was proposed to evaluate the interaction ability of cement-emulsified asphalt. The results show that the cement-emulsified asphalt interaction is merely a physical blending process due to the occurrence of no new characteristic peaks in the FTIR spectrum except for cement hydration products. The cement-emulsified asphalt interaction in early-age CEACB could be reflected by the aggregation process among asphalt droplets and the adsorption action of cement particles to asphalt droplets. A reasonable ratio of cement to emulsified asphalt could promote the formation of the denser spatial network structure of CEACB along with cement hydration products growing and interweaving with asphalt films. The K-B-G* index based on macro-rheological properties of CEACB with full consideration of cement hydration process is very suitable for evaluating the interaction ability of cement-emulsified asphalt under the condition of different cement proportions and curing time. The research would provide the support for understanding the natural properties of CEACB and promote the improvement of the mechanical performance of cold recycled asphalt pavements.