Long-term observation of the triboelectric effect has not only proved the feasibility of many novel and useful tribo-devices (e.g., triboelectric nanogenerators), but also constantly motivated the exploration of its mysterious nature. In the pursuit of a comprehensive understanding of how the triboelectric process works, a more accurate description of the triboelectric effect and its related parameters and factors is urgently required. This review critically goes through the fundamental theories and basic principles governing the triboelectric process. By investigating the difference between each charging media, the electron, ion, and material transfer is discussed and the theoretical deduction in the past decades is provided. With the information from the triboelectric series, interesting phenomena including cyclic triboelectric sequence and asymmetric triboelectrification are precisely analyzed. Then, the interaction between the tribo-system and its operational environment is analyzed, and a fundamental description of its effects on the triboelectric process and results is summarized. In brief, this review is expected to provide a strong understanding of the triboelectric effect in a more rigorous mathematical and physical sense.