The Accelerator Neutrino Neutron Interaction Experiment (ANNIE) is a 26-ton water Cherenkov neutrino detector installed on the Booster Neutrino Beam (BNB) at Fermilab. Its main physics goals are to perform a measurement of the neutron yield from neutrino-nucleus interactions, as well as a measurement of the charged-current cross section of muon neutrinos. An equally important focus is placed on the research and development of new detector technologies and target media. Specifically water-based liquid scintillator (WbLS) is of interest as a novel detector medium, as it allows for the simultaneous detection of scintillation and Cherenkov light. This paper presents the deployment of a 366L WbLS vessel in ANNIE in March 2023 and the subsequent detection of both Cherenkov light and scintillation from the WbLS. This proof-of-concept allows for the future development of reconstruction and particle identification algorithms in ANNIE, as well as dedicated analyses, such as the search for neutral current events and the hadronic scintillation component within the WbLS volume.