The longitudinal spin Seebeck effect (SSE) in Bi2O3/Cu/yttrium-iron-garnet (YIG) devices has been investigated. When an out-of-plane temperature gradient is applied to the Bi2O3/Cu/YIG device, a spin current is generated across the Cu/YIG interface via the SSE and then converted into electric voltage due to the spin-orbit coupling at the Bi2O3/Cu interface. The sign of the SSE voltage in the Bi2O3/Cu/YIG devices is opposite to that induced by the conventional inverse spin Hall effect in Pt/YIG devices. The SSE voltage in the Bi2O3/Cu/YIG devices disappears in the absence of the Bi2O3 layer and its thermoelectric conversion efficiency is independent of the Cu thickness, indicating the important role of the Bi2O3/Cu interface. This result demonstrates that not only the bulk inverse spin Hall effect but also the spin-orbit coupling near the interface can be used for SSE-based thermoelectric generation.