CAlcium fluoride for the study of Neutrinos and Dark matters by Low-energy Spectrometer (CANDLES) is searching for neutrino-less double-beta decay of 48 Ca using a CaF 2 scintillator array. A high Q-value of 48 Ca at 4,268 keV enabled us to achieve low background, however, at the same time it causes difficulties in calibrating the detector's Q-value region because of the absence of a standard high-energy γ-ray source. Therefore, we have developed a novel calibration system based on γ-ray emission by neutron capture on 28 Si, 56 Fe, and 58 Ni nuclei. In this paper, we report the development of the new calibration system as well as the results of energy calibration in CANDLES up to 9 MeV.