We report the measurement of the inhomogeneous linewidth, homogeneous linewidth, and spin-state lifetime of Pr3+ ions in a novel waveguide architecture. The TeO2 slab waveguide deposited on a bulk Pr3+∶Y2SiO5 crystal allows the 3H4↔1D2 transition of Pr3+ ions to be probed by the optical evanescent field that extends into the substrate. The 2-GHz inhomogeneous linewidth, the optical coherence time of 70±5 μs, and the spin-state lifetime of 9.8±0.3 s indicate that the properties of ions interacting with the waveguide mode are consistent with those of bulk ions. This result establishes the foundation for large, integrated, and high performance rare-earth-ion quantum systems based on a waveguide platform.