The relevant excited state for T-shaped and α-diimine Pd complexes can potentially decay through radiative (fluorescence) or other nonradiative decay (NRD) pathways (i.e., solvent-mediated) that do not lead to radical formation, in addition to the pathway resulting in Pd(II)-C homolytic cleavage. One of the former two processes might explain the discrepancies in quantum yield we observe for methyl radical formation from either 1a or 3 if its relative rate is fast enough to dominate the fate of the complex's excited state. We investigated the luminescence properties of these complexes to test this hypothesis. Luminescence measurements were complicated by sample decomposition due to the Pd(II)-C homolysis process, as determined by changes in the absorption spectra even after a single scan. As such, data were collected using low beam power and the sample solution was replenished between each scan to minimize the influence of sample decomposition. Features consistent with fluorescent emission were not detected from either 1a or the α-diimine complex 3.