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A transparent glass ceramic (GC) is designed via the controllable precipitation of KYb3F10 nanocrystals. It is shown that the crystallization in GC deeply depends on the doping of Yb3+. Yb3+ ions are spontaneously distributed in the fluoride crystal environments without the ionic substitution process of traditional GC. As a result, high-efficiency upconversion (UC) luminescence is achieved in GC. The UC quantum yield value of the Yb3+-Er3+-codoped GC is as high as 1.44±0.02%, which is more than 20 times higher than the traditional GC co