Entropy is a state function of the real physical system, which relates to the chaos of a system. During the long-term exploring glass-forming systems, many empirical rules are put forward, including “confusion principle” and three empirical rules.Over a long period of exploring, many glass-forming alloys are developed based on those principles, while some questions have been raised in recent years based on the experimental results, because some other uncertain factors also have influence on the glass-forming ability (GFA) except a number of constituents, e.g., entropy. Greer claimed that in the “confusion principle” the higher the entropy value, the better the glass-formation ability will be, which does not accord with the recent experimental results.The effects of entropy on the glass-formation ability are summarized from the viewpoints of thermodynamics, kinetics, and complexity of atomic structures. In the aspects of thermodynamics and structure, the increase of entropy has a positive effect on glass formation, while in kinetics, the influence is negative. From the viewpoint of thermodynamics, the increase of entropy leads to the decrease of the entropy difference between solid phase and liquid phase, and therefore, the difference in Gibbs free energy between these two phases decreases. At a certain time during solidification, compared with the low-entropy alloy, the high-entropy alloy in the solid phase has an atomic arrangement close to that in the liquid, and it is more likely to form the amorphous phase.In the aspect of kinetics, the increase of entropy results in the decrease of the viscosity of the system according to the Adam-Gibbs equation. As a result, atoms diffuse easily in the system and the ordered-phase is more likely to form, which means that the glass-formation ability decreases with the increase of entropy. Furthermore, in the aspect of atomic structure, the increase of mismatch entropy relates to the big misfit degree between atoms, i. e., the large atomic size difference. Atoms in the high-entropy alloy tend to distribute disorderly in the system, and therefore the stress between atoms increases. As a result, with the increase of the entropy, the ordered-phase becomes unstable and the GFA will be enhanced.Furthermore, the high-entropy-glass is briefly reviewed and analyzed, which is a new system between high-entropy alloy and amorphous alloy. There have been many high-performance high-entropy-glass systems reported up to now. Researches about this unique system will contribute to developing some new amorphous alloys with excellent performances, and more importantly, to exploring the complex relationship between GFA and multicomponent alloys.