We present a non-destructive optical technique for a full characterization of rare-earth-doped optical preforms. Specifically, a combined profiling of refractive-index and active-dopant was carried out in the same region of optical preforms by performing ray deflection and photoluminescence projection measurements, respectively. In this way, the optical core, delineated by the refractive index profile, was used to define the actual active dopant distributions within the core. Using the same experimental set-up, it was also possible to uniquely provide the maximum value of active-ion concentration reached inside the core. The study was carried out on an optical fiber preform sample doped with Yb3+ ions in high concentration. Comparison with independent measurements, such as those performed by a commercial refractive index profiler and microstructural secondary-ion mass spectrometry analysis, confirms the …