Mg metal reduction of the divalent precursor PdCl2(CNArDipp2)(2) (Dipp = 2,6-diisopropylphenyl) provides the isolable, two-coordinate Pd(0) bis-isocyanide, Pd(CNArDipp2)(2), which is the first stable monomeric isocyanide complex of zerovalent palladium. Variable temperature H-1 NMR and FTIR studies on Pd(CNArDipp2)(2) in the presence of added CNArDipp2 revealed that free and coordinated isocyanide undergo rapid exchange, but the components do not form a stable tris-isocyanide complex. Bis-isocyanide Pd(CNArDipp2)(2) is active for oxidative addition reactions and readily reacts with benzyl chloride and mesityl bromide to form Pd(Cl)(Bz)(CNArDipp2)(2) and Pd(Br)(Mes)(CNArDipp2)(2), respectively. Room-temperature Suzuki-Miyaura cross-coupling reactions are mediated by Pd(CNArDipp2)(2). Coordinatively and electronically unsaturated substrates also react with Pd(CNArDipp2)(2). Addition of thallium(I) triflate (TlOTf) to Pd(CNArDipp2)(2) results in the salt [TlPd(CNArDipp2)(2)]OTf, while addition of O-2 results in the peroxo complex (eta(2)-O)Pd(CNArDipp2)(2). Most remarkably, 2 equiv of nitrosobenzene react with Pd(CNArDipp2)(2) to form the square planar complex (kappa(1)-N-PhNO)(2) Pd(CNArDipp2)(2), the geometry of which strongly suggests the formation of a divalent Pd center. With the aid of density functional theory calculations, this valence change is rationalized in terms of a formal reduction of the bond order-in each NO unit to 1.5.