The sensitive and rapid detection of thermal neutrons holds significant importance in various fields such as energy utilization, medical treatment, and national defense. However, the available thermal neutron scintillator is difficult to reach this target, mainly limited by the optical and scintillating performance. Herein, the in situ crystallization strategy of glass to construct scintillation glass composites for efficient thermal neutron detection is proposed. The congruent crystallization of the hybridized alkali earth silicate glass system may not only achieve high crystallinity, but also will keep the refractive indexing matching between the precipitated crystal and precursor glass phases. The prepared glass composites feature high luminescence efficiency, optical transmission and excellent neutron response properties. These factors collectively contribute to the robust neutron scintillation performance with a light output of ≈36 000 photons/neutron, which represents the highest value among glass‐based scintillators. Moreover, the composite configuration brings about the additional function of thermal neutron and γ‐ray discrimination. By using this composite scintillator, the neutron detector is constructed and demonstrates its application for detecting thermal neutron and distinguishing it from γ‐ray in an online way. The studies prove that glass composites with high crystallinity are expected to be promising candidates for a new generation of multifunctional neutron detectors.