The ground electronic states of PdCO-/PdCN and PdCN-/PdCN are investigated using anion photoelectron spectroscopy (PES). The electron affinity of PdCO- is determined to be 0.604 +/- 0.010 eV. The anion PES of PdCO- exhibits a single, vibrationally resolved electronic band assigned to the (1)Sigma(+) + e(-) <--(2)Sigma(+) anion to neutral transition. The neutral carbonyl stretch is resolved and measured to be 2140 +/- 660 cm(-1). There is an additional, partially resolved 350 +/- 40 cm(-1) vibrational progression that is attributed to Pd-CO relative motion. The PES of PdCN- exhibits a single peak at 2.543 +/-0.007 eV, which is the electron affinity of PdCN. This vertical electronic band is tentatively assigned to the (2)Sigma(+) + e(-) <-- (1)Sigma(+) transition. The highest occupied molecular orbital of both the anion and neutral is described as a nonbonding spd hybrid orbital on Pd that does not affect the ionic bond of the neutral Pd+. CN- core. The various reactions of Pd and Pd- with methanol and acetonitrile along with other reactants that may be present in the ion source are considered.