We report, for the first time, structural transformation and photoluminescence behavior by calcination of layered europium-doped yttrium hydroxide (LYH:Eu) intercalate with organic sensitizer terephthalate (TA). The calcined samples displayed tunable luminescent performance dependent on calcined temperatures. Calcination under low temperatures (200 and 300°C) retained layered structure, while high temperatures (>400°C) yielded oxide phase. The optimal fluorescence occurred in 200°C-calcination, possibly resulting from an optimal arrangement of TA. Above 200°C, the luminescence intensity was first weakened and then enhanced, due to gradual departure of TA and following occurrence of oxide phase. The energy transfer presented an intrinsic transition from TA-to-Eu3+ in the organic intercalate to O2−-to-Eu3+ charge transfer in as-transformed oxide. The predominant luminescence property of the hybrid material can provide valuable guide for developing tunable luminescent materials, especially flexible materials resulting from the containing organic component.