Channel waveguides with diffraction gratings at their input and output for light injection and extraction, respectively, are extensively exploited for optical and photonic applications. In this paper, we report for the first time on such an architecture on glass entirely elaborated by sol–gel processing using a titanium-oxide-based photoresist that can be imprinted through a single photolithography step. This work is more particularly focused on a fluorescent architecture including channel waveguides doped with a ruthenium-complex fluorophore (tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II), Rudpp). The study demonstrates that this original sol–gel micro-structured architecture is well adapted to efficient channel waveguide/diffraction grating coupling and propagation of the fluorescence excitation and emission signals in the core of the channel waveguide. It demonstrates, in particular, a relatively large tolerance of several degrees in the angular injection fiber positioning and an important axial and vertical fiber spatial positioning tolerance of more than 100 µm at the Rudpp emission wavelength. The measurements also indicate that, in the conditions tested in this work, a Rudpp concentration of around 0.1 mM and a channel waveguide length of 2 to 5 mm offer the best trade-off in terms of excitation signal propagation and emission signal detection. This work constitutes a promising preliminary step toward the integration of our architecture into a microfluidic platform for fluorescence measurement in a liquid medium and waveguiding configuration.