This paper demonstrates the electrocaloric effect (ECE) around BaTiO3's orthorhombic-tetragonal first-order phase transition. By manipulating a field-induced transition of a metastable phase in the thermal hysteresis zone, a huge exothermic or endothermic peak appears after first applying or removing electric fields because of the energy change of lattice structure. A large ECE of ΔT/E = 1.4K·m/MV, equaling to latent heat, is achieved under 10kV/cm at 10°C. The entropy change for polarization ordering alone induces an ECE two orders of magnitude lower under the same condition. It confirms the dominant factor to ECE of the energy flow due to the structural phase transition.