Spectra of optical transitions to excited electronic states in RaF in the form of PGOPHER overlay files (.ovr extension). The results of the analysis of these spectra will be published in the article Electron correlation and relativistic effects in the excited states of radium monofluoride (2025) in Nature Communications. The spectra were obtained using the Collinear Resonance Ionization Spectroscopy (CRIS) experiment at the CERN-ISOLDE radioactive ion beam facility. Information on the CRIS experiment applied to radioactive molecules can be found in the Methods section of the article: M. Athanasakis-Kaklamanakis, S. G. Wilkins, L. V. Skripnikov, et al., Electron correlation and relativistic effects in the excited states of radium monofluoride, Nature Communications (2025). See authors of the manuscript for a complete list of contributors to this dataset, and acknowledgment of relevant grants. Contacts about the dataset: Michail Athanasakis-Kaklamanakis, m.athkak@cern.ch Shane G. Wilkins, wilkinss@mit.edu Gerda Neyens, gerda.neyens@kuleuven.be