The study on natural aging of fiber reinforced composite, delamination damage behavior and damage pattern recognition plays a significant role in structural health monitoring of the material. In this study, acoustic emission is used to investigate damage evolution process and damage mechanisms in unidirectional glass and carbon-glass orthogonal woven fiber reinforced composites containing symmetric multiple delaminations under three point bending testing. Based on the principle of control variables, four kinds of specimens are manufactured to investigate the comparative study for the effects of delaminations, reinforced materials and fiber orientation on buckling failure behaviors and the effects of aging on mechanical properties. The results indicate that the degradation of strength and stiffness of composite can be influenced by the existence of delamination defects and natural aging condition. Both negative and positive effects can be generated by natural aging condition. Moreover, reinforced materials, porosity and fiber orientation are important factors influencing the reliability of composite. Clustering results of unidirectional fiber reinforced composites indicate interphase failure is the main damage component, moreover, the existence of symmetrical multiple delaminations will aggravate the damage of composite and make instability failure characterized by intermittency.