The first crystallographic characterization of an iron carbonyl dihydride H2Fe(CO)(2)[P(OPh)(3)](2) has been performed. The complex has a distorted octahedral geometry with two triphenylphosphite ligands trans to each other and the carbonyl ligands cis to each other. The two other equatorial sites are occupied by two cis hydrides. Mossbauer spectra and thermal behavior of H2Fe(CO)(2)[P(OPh)(3)](2) are also reported and compared with those of related complexes.