Triacylglycerols (TAGs) exhibit a monotropic polymorphism, forming three main polymorphic forms upon crystallization: α, β’ and β. The distinct physicochemical properties of these polymorphs, such as melting temperature, subcell lattice structure, mass density, etc., significantly impact the appearance, texture, and long-term stability of a wide range products in the food and cosmetics industries. Additionally, TAGs are also of special interest in the field of controlled drug delivery and sustained release in pharmaceuticals, being a key material in the preparation of solid lipid nanoparticles. The present article outlines our current understanding of TAG phase behavior in both bulk and emulsified systems. While our primary focus are investigations involving monoacid TAGs and their mixtures, we also include illustrative examples with natural TAG oils, highlighting the knowledge transfer from simple to intricate systems. Special attention is given to recent discoveries via X-ray scattering techniques. The main factors influencing TAG polymorphism are discussed, revealing that a higher occurrence of structural defects in the TAG structure always accelerates the rate of the α → β polymorphic transformation. Diverse approaches can be employed based on the specific system: incorporating foreign molecules or solid particles into bulk TAGs, reducing drop size in dispersed systems, or using surfactants that remain fluid during TAG particle crystallization, ensuring the necessary molecular mobility for the polymorphic transformation. Furthermore, we showcase the role of TAG polymorphism on a recently discovered phenomenon: the creation of nanoparticles as small as 20 nm from initial coarse emulsions without any mechanical energy input. This analysis underscores how the broader understanding of the TAG polymorphism can be effectively applied to comprehend and control previously unexplored processes of notable practical importance.