The entropy mediated temperature‐structure evolution has attracted significant interest, which is used for the development of functional alloys and ceramics. But such strategy has not yet been demonstrated for development of non‐metallic glasses. Herein, the successful application of the entropy engineering concept to non‐metallic glass to manipulate its in situ crystallization process is demonstrated. The comparison of the entropy concept in alloys, ceramics, and non‐metallic glass is discussed. As a typical example, the activation and preservation of the entropy stabilized effect of a typical niobosilicate glass system at different temperatures are studied. The relation between the micro‐configurations and the entropic property is analyzed. Via the entropy engineering strategy, the crystallization of the niobosilicate glass can be manipulated. As a result, the LiNbO3 nanocrystal‐in‐glass (NiG) composite with high crystallinity is developed, which exhibits 8 times higher nonlinearity compared with the β‐BBO crystal. The developed NiG composite is demonstrated for practical application in precise measurement of the duration and phase of ultra‐short femtosecond pulse.