[Ir(ppy)(2)(5-R-1,10-phen)][PF(6)] (ppy = cyclometallated 2-phenylpyridine, phen = phenanthroline, R = H, Me, NMe(2), NO(2)) and [Ir(ppy)(2)(4-R',7-R'-1,10-phen)][PF(6)] (R' = Me, Ph) complexes are characterized by one of the highest second order NLO response (measured by the EFISH technique) reported for a metal complex, mainly due (as suggested by a theoretical SOS-TDDFT investigation) to MLCT processes from the ppy-Ir based moiety acting as donor push system to pi* orbitals of phen, acting as an acceptor pull system; the good transparency to the second harmonic emission renders these NLO-phores appealing as building blocks for molecular materials with second harmonic generation.