We report first evidence of wakefield acceleration of a relativistic electron beam in a dielectric-lined slab-symmetric structure. The high energy tail of a ∼60 MeV electron beam was accelerated by ∼150 keV in a 2 cm-long, slab-symmetric SiO2 waveguide, with the acceleration or deceleration clearly visible due to the use of a beam with a bifurcated longitudinal distribution that serves to approximate a driver-witness beam pair. This split-bunch distribution is verified by longitudinal reconstruction analysis of the emitted coherent transition radiation. The dielectric waveguide structure is further characterized by spectral analysis of the emitted coherent Cherenkov radiation at THz frequencies, from a single electron bunch, and from a relativistic bunch train with spacing selectively tuned to the second longitudinal mode (TM02). Start-to-end simulation results reproduce aspects of the electron beam bifurcation dynamics, emitted THz radiation properties, and the observation of acceleration in the dielectric-lined, slab-symmetric waveguide.