The characterization of a wide range of luminescent thin films can be a long and tedious endeavor. With reactive combinatorial sputtering of multiple metal targets, it possible to fabricate thin films with a gradient in composition simply by not rotating the substrate. In this work, combinatorically sputtered thin films of Cr3+ and Nd3+ doped in the Al2O3–Y2O3 system (YAlO) are studied for thin film based luminescent solar concentrators (TFLSCs) application. Contrary to mm's thick plate type LSC's, TFLSCs of just several 100 nm thick require much higher Cr3+ concentration to achieve 40% absorption which can enable several 10's of W/m2 LSC power efficiencies. Our transmission measurements on a Cr2O3 film with a thickness gradient result in an absorption cross section at 460 nm of 1.3 ± 0.7 × 10−19 cm2 showing that the TFLSC absorption requirement can be fulfilled provided that the Cr3+ concentration is in the order of 1022 ions/cm3. The Y:Al ratio of the YAlO host in our films ranged between 0.5 and 3.5, thereby including the monoclinic (Y4Al2O9), perovskite (YAlO3) and garnet (Y3Al5O12) stoichiometry's on a single film. Position dependent XRD, EDX, excitation, emission and lifetime measurements of Cr3+ and Nd3+ show that the unique gradient film sputtering method is able to characterize thin films as a function of host composition and doping concentration. Energy transfer between Cr3+ and Nd3+ in co-doped YAlO films is concluded from Cr3+ excitation bands observed while monitoring Nd3+ emission and from the matching of the rise-time of Nd3+ 1340 nm emission (4F3/2 ->4I11/2) and the decay time of Cr3+ 840 nm emission (4T2 ->4A2). Nd3+ lifetime systematically decreases from 0.24 to 0.05 ms with increasing Cr3+ concentration in Y3Al5-xCrxO12:Nd (0.05 < x < 2). The constraints of heavily doped Cr3+ thin films for enabling adequate absorption and energy transfer to Nd3+ in TFLSC applications are the subjects of the discussion.