Cyclopalladated azido dimers having various C,N-donor ligands, [Pd(μ-N3)(C,N-Ln)]2 (L1H = 2-(2′-thienyl)pyridine; L2H = azobenzene; L3H = 3,3′-dimethylazobenzene; L4H = N,N′-dimethylbenzylamine; L5H = 2-phenylpyridine), underwent cleavage with tertiary (or chelating) phosphines to form the cyclopalladated [Pd(N3)(PR3)(C,N-L)], the σ-bonded [Pd(N3)(PR3)2(C-L)], or the dinuclear-cyclopalladated [PdN3(PR3)(C,N-L)]2(μ-P∼P) complexes. In particular, treating [Pd(μ-N3)(C,N-L)]2 with the basic chelating phosphine (depe or dmpe) produced the homoleptic bis(chelating) complex [Pd(C,N-Ln)2] (n = 1–3). Complex [Pd(N3)(PR3)(C,N-L4)] or [Pd(N3)(PR3)2(C-L4)] reacted with aryl isocyanides to selectively give the imidoyl [Pd(N3)(–CN–Ar)(PR3)(N-L4)] or the imidoyl carbodiimido complex [Pd(NCN–Ar)(–CN–Ar)(PR3)(N-L4)], which was formed by the CN–Ar insertion into the orthometallated Pd–C bond on the phenyl moiety or the interaction into the Pd–N3 bond of the supporting ligand. In addition, reactions of [Pd(N3)(PR3)2(C-Ln)] (n = 1, 2, 4) with R–NCS {R = i-Pr, C6H4–NCS, (CH3)3Si} gave the S-coordinated tetrazole–thiolato Pd(II) complexes. Finally, the catalytic activity of the cyclopalladated azido complexes was evaluated.