There is very limited research in the literature investigating the way acoustic emission signals change when polymer materials are undergoing different fracture modes. This study investigates the capability of acoustic emission to recognize the fracture mode through acoustic emission parameter analysis, and can be considered the first-ever study which examines the impact of different loading conditions, i.e., fracture mode I, mode II, and mode III, on the acoustic emission parameters in polymer materials. To accomplish this, prism-like pre-cracked polymer specimens were tested under the three different fracture modes. Acoustic emission parameters appeared sensitive to the different loading conditions of the pre-cracked specimens, indicating that acoustic emission can be used to distinguish the three fracture modes in polymer materials. Both frequency and time parameters reflect changes in the stress states at the crack tip. The duration and rise time of the waveforms were found to be the most sensitive acoustic emission parameters for identifying the fracture mode, while the average frequency variation can be employed to differentiate between in-plane and out-of-plane fracture modes. In order to interpret the experimental results in relation to wave mechanics, numerical wave propagation simulations for longitudinal and shear excitations were performed to simulate tensile and shear fracture modes and the corresponding emitted waves. An interesting correlation between the experimental and numerical results exists, showcasing acoustic emission’s potential for fracture identification.