This study introduces a comprehensive set of designed and tested glass/epoxy composites, AE monitoring and signal processing techniques; (i) to investigate the effect of multiple delaminations on buckling and post-buckling behaviors of laminated composites and (ii) to evaluate Acoustic Emission (AE) technique ability to monitor the buckling delamination growth and to classify the occurred damage mechanisms. The pre-delaminations were made by inserting a Teflon film at the plies interfaces during fabrication. Three different types of specimens were fabricated and subjected to compression loading to study the effects of the location, the number of delaminations, and the thickness of the Teflon film on buckling and post-buckling behaviors of the specimens. The mechanical results showed that the number of delaminations has a major effect on the critical and maximum loads and the location of delamination and the thickness of the Teflon film have minor effects on the critical and maximum loads. The AE signals of the specimens were then classified using Gaussian Mixture Model (GMM) and the evolution of different damage mechanisms was investigated. The AE results showed that AE is a robust technique to classify damage mechanisms in buckling of laminated composites and could identify delamination propagation earlier and with a lower standard deviation, compared with the conventional methods.