A liquid/liquid optical waveguide was constructed using a sheath flow. Since the refractive index of an organic solvent is generally higher than that of water (<i>n</i><sub>D</sub> = 1.33), light introduced into the inner organic flow should proceed with total multi-reflection within the inner flow, so that the inner part of the sheath flow acts as the core of an optical waveguide. This sheath flow liquid/liquid optical waveguide was stable and showed no substantial background scattering. Moreover, it is applicable to both miscible and immiscible liquid/liquid interfaces. Thus, it may become a new tool for studying liquid/liquid interfaces as well as for sensitive optical measurements.

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