At radioactive ion beam facilities like ISOLDE at CERN, a high purity of the element of interest in the ion beam is essential for most experiments on exotic nuclei. Due to its unique combination of high ionization efficiency and ultimate elemental selectivity, the Resonance Ionization Laser Ion Source, RILIS, has become the most frequently used ion source at ISOLDE and at the majority of similar facilities worldwide. However, isobaric contamination predominantly stemming from unspecific surface ionization may still introduce severe limitations. By applying the highly selective resonance ionization technique inside a radio-frequency quadrupole ion guide structure, the novel approach of the Laser Ion Source and Trap, LIST, suppresses surface ionized isobaric contaminants by an electrostatic repelling potential. Following extensive feasibility studies and off-line tests, the LIST device has been adapted and refined to match the stringent operational constraints and to survive the hostile environment of the ISOLDE front-end region enclosing the highly radioactive nuclear reaction target. The LIST operation was successfully demonstrated for the first time on-line at ISOLDE during two experiments, attesting its suitability for radioactive isotope production under routine conditions. Data of these on-line characterization measurements confirm a suppression of surface-ionized isobars by more than a factor of 1000 in accordance to off-line studies that were carried out for the preparation of the on-line experiments. During the first on-line test, the suppression was associated with an efficiency loss of not more than a factor of about 50 with respect to normal RILIS operation. These losses could be further reduced to only about 20 during the second run. Results of the off-line studies in comparison to the first on-line characterization data are discussed here