The synthesis of C∧C∧P pre-ligands based on a dicyclohexylphosphine-substituted biphenyl framework is reported. The pre-ligands form the respective non-palindromic pincer complexes of PtII and PdII via double oxidative addition and subsequent comproportionation or C-H activation. The complexes of PtII as well as PdII emit similar green phosphorescence efficiently in the solid state, the former also in solution albeit with less intensity. The most fascinating photophysical feature, however, is a direct singlet-triplet (S0 → T1) excitation of this phosphorescence in the spectral window between the emission and the major singlet-singlet UV absorption. The S0 → T1 excitation spectra show a rich vibronic pattern, which is especially pronounced for the solid samples at cryogenic temperatures. The molar extinction of the lowest-energy singlet-triplet absorption band of the homologous Pt and Pd complexes as well as that of the Pt complex with a different (NHC) ancillary ligand were determined in tetrahydrofuran solutions. Quantum efficiencies of triplet formation (by intersystem crossing) via the "standard" excitation pathway S0 → Sn → T1 were determined for the Pt complexes and found to be different in dependence of the ancillary ligand.