The study on acoustic emission characteristics of the bi-material made of concrete and rock under loading condition can provide a scientific basis for predicting rupture instability of this material. Thus, some relevant experiment works on concrete, rock and bi-material were carried out which were for probing into acoustic emission characteristics. Through our experiments, the following results are obtained. For bi-material, double peaks are clearly presented in the energy count curve during rupture evolution process, and the first peak can be used for predicting its instability. The spatial-temporal evolution law of acoustic emission events indicate that unsteady rupture development of the bi-material firstly begins with the concrete, then the rock material is into unstable state via cementation surface. The clustering results of AE location indicate that shearing instability firstly occurs in the concrete, then the kinetic energy released by fracture instability and stress concentration of the aggregate induce the fracture of rock material.