The design and characterization of thermally activated delayed fluorescence (TADF) materials for optoelectronic applications represents an active area of recent research in organoelectronics. Noble metal‐free TADF molecules offer unique optical and electronic properties arising from the efficient transition and interconversion between the lowest singlet (S1) and triplet (T1) excited states. Their ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T1→S1) could directly impact their properties and performances, which is attractive for a wide variety of low‐cost optoelectronic devices. TADF‐based organic light‐emitting diodes, oxygen, and temperature sensors show significantly upgraded device performances that are comparable to the ones of traditional rare‐metal complexes. Here we present an overview of the quick development in TADF mechanisms, materials, and applications. Fundamental principles on design strategies of TADF materials and the common relationship between the molecular structures and optoelectronic properties for diverse research topics and a survey of recent progress in the development of TADF materials, with a particular emphasis on their different types of metal‐organic complexes, D‐A molecules, and fullerenes, are highlighted. The success in the breakthrough of the theoretical and technical challenges that arise in developing high‐performance TADF materials may pave the way to shape the future of organoelectronics.