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This letter describes all-liquid optical waveguiding within microfluidic channels that employs viscosity-mismatched core and cladding fluids. Efficient optical coupling is achieved through superior control of fluid flow profiles obtained via hydrodynamic focusing and models describing the control of the viscosity-mismatched, graded index fluid waveguides are presented. As a demonstration of this approach, a fluorescence quantification assay is performed using dyed colloidal particles.