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Abstract 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 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 Cherenkov light and scintillation. This paper presents the deployment of a 366 L 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 within the WbLS volume, such as the search for neutral-current events and the hadronic scintillation component.