This paper presents the results of an investigation into autoionizing states of atomic chromium, in the service of the resonance ionization laser ion source (RILIS): the principal ion source of the ISOLDE radioactive ion beam facility based at CERN. The multi-step resonance photo-ionization process enables element selective ionization which, in combination with mass separation, allows isotope specific selectivity in the production of radioactive ion beams at ISOLDE. The element selective nature of the process requires a multi-step “ionization scheme” to be developed for each element. Using the method of in-source resonance ionization spectroscopy, an optimal three-step, three-resonance photo-ionization scheme originating from the 3d5(6S)4s a7S3 atomic ground state has been developed for chromium. The scheme uses an ionizing transition to one of the 15 newly observed autoionizing states reported here. Details of the spectroscopic studies are described and the new ionization scheme is summarized. •An investigation of multi-resonance photo-ionization schemes for Cr I•15 new autoionizing states of Cr I observed•The optimal scheme had an estimated ionization efficiency of 20%.•Laser ionized radioactive Cr ion beams now available at the CERN-ISOLDE facility Display omitted