AbstractSolid‐state caloric effects as intrinsic thermal responses to different physical external stimuli (magnetic‐, uniaxial stress‐, pressure‐, and electric‐fields) can achieve a higher energy efficiency compared with traditional gas compression techniques. Among these effects, magnetocaloric energy conversion is regarded as the best available alternative and has been exploited extensively for promising application scenarios in the last decades. This review systematically introduces the magnetocaloric effect and its applications, and summarizes the corresponding representative magnetocaloric materials, as well as important progress in recent years. Specifically, the review focuses on some key understandings of the magnetocaloric effect by utilizing state‐of‐the‐art technical tools such as synchrotron X‐ray, neutron scattering, muon spin spectroscopy, positron annihilation spectroscopy, high magnetic fields, etc., and highlights their importance toward advanced materials design and development. An overview of the basic principles and applications of these advanced techniques on magnetocaloric materials is provided. Finally, the challenges and perspectives on further developments in this field are discussed. Further in‐depth understanding and manufacturing technology advancement combined with fast‐developed artificial intelligence and machine learning are expected to advance the magnetocaloric energy conversion technology closer to real applications.