Direct reaction between the hydroxo-complexes [{Pd(μ-OH)(C^N)} 2 ] (C^N=2-(2-pyridyl)phenyl (Phpy) I; C^N=7,8-benzoquinolyl (Bzq) II) and N-naphtylsalycilaldimine (N-naphsal) 1 yields new mononuclear cyclometallated palladium(II) complexes [Pd(N-naphsal)(C^N)] (I1, II1). Photophysical properties were investigated together with those of complexes with related ligands N-phenylsalycilaldiminate (N-Phsal) 2, N-p-chlorophenylsalycilaldiminate (N-pClPhsal) 3. All the compounds absorb intensely below 300nm via 1 LC transitions located in Bzq or Phpy ligands, and display additional low energy absorptions of mixed 1 MLCT– 1 LC character. The complexes under study are quite unusual in terms of luminescence behavior, since some of them are emissive in solution at room temperature and all display intense emissions in frozen CHCl 3 solution, but also in solid state at 298 and 77K. Structural characterization by X-ray diffraction of complexes I2, I3 and II2 confirmed the proposed formulae.