The local atomic and electronic structures of ${\mathrm{La}}_{0.7}{\mathrm{Ca}}_{0.3}\mathrm{Mn}{\mathrm{O}}_3$ (LCMO) prepared by solid-state reaction was investigated at different annealing temperatures $\left(T_A\right)$ . We employed x-ray absorption spectroscopy and x-ray photoemission spectroscopy to understand the local atomic and electronic structures of the LCMO system. Both the atomic and electronic structures due to the oxygen deficiency in LCMO turn out to change with increasing $T_A$ . Especially, the $e_g$ ↑ states, leading to the ferromagnetic interaction, are reduced by the diminution of Mn $3d–\mathrm{O}$ $2p$ hybridization with increasing $T_A$ .