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We report first read out result of inorganic-organic hybrid scintillator; Ce:LiCaAlF6 single crystal covered with plastic scintillator for neutron detection. The Ce:LiCaAlF6 sample coated with POPOP containing PPO showed great light output and energy resolution than the Ce:LiCaAlF6 itself when it was coupled to PMT. Light output was increased up to 203% and energy resolution was improved to 9%, which originally it was 16%. Moreover, we succeed in clear neutron peak this new hybrid scintillator APD (Hamamats S8664-1010).