In this study, acoustic emission (AE) technique is used to investigate different time-to-failure mechanisms of delamination in glass/epoxy composite laminates. Woven and unidirectional layups were subjected to the double cantilever beam, end notch flexure, and mixed-mode bending tests and the generated AE signals were captured. Discrimination of the AE events, caused by different types of the damage mechanisms, was performed using wavelet packet transform (WPT) and fuzzy clustering method (FCM) associated with a principal component analysis (PCA). The FCM and WPT analyses identified three dominant damage mechanisms. Furthermore, different interface layups and different GII/GT modal ratio values (ratio of mode II strain energy release rate per total strain energy release rate) indicated different time-to-failure mechanisms incidence. Additionally, the damaged mechanisms were observed using scanning electron microscopic (SEM) analysis. The results showed that the dominant damage mechanisms in all the specimens are matrix cracking and fiber–matrix debonding. Besides, some fiber breakage appeared during the tests, and the percentage of this damage mechanism in the unidirectional specimens and mode I condition was higher than those in the woven specimens and mode II. SEM observations were also in good agreement with the obtained results. It was found that the presented methods can be utilized to improve the characterization and discrimination of damage mechanisms in the actual occurring modes of delamination in composite structures.