LnBaCo2O5+delta (Ln-112) where Ln = lanthanide element; 0 smaller or equal to delta smaller or equal to1 and LnBaCo4O7+delta (Ln-114) are highly correlated cobalt oxides. Synchrotron photoemission spectroscopy of LnBaCo2O5+delta (Ln = Gd, Dy, Dy1-xTbx) and LnBaCo4O7 (Ln = Yb) has been undertaken at the UK Synchrotron Radiation Source (Daresbury Laboratory).During the photoemission experiments, the samples were observed to be contaminated due to residual gases inside the main vacuum chamber. The surface degradation of the samples is studied using the difference spectra generated from the valence band spectra of freshly scraped and contaminated samples and the nature of contaminated species on these samples is identified in the light of the reviewed literature.High-resolution photoemission is carried out to study the metal-insulator (MI) transition in double perovskites LnBaCo2O5+delta (Ln = Gd, Dy, Dy1-xTbx - Ln-112; 0 smaller or equal to delta smaller or equal to 1) as a function of temperature. The high-resolution photoemission results of single crystal samples of GdBaCo2O5.5, DyBaCo2O5.5 and Dy1-xTbxBaCo2O5+ show that the temperature-based MI transitions in these compounds occur in the 300-400 K temperature range. A post-growth oxygen annealing treatment for as-grown single crystals of Ln-112 is necessary, achieving oxygen contents close to 5.50, to observe a marked nonmetal-to-metal transition. Resonant photoemission is used to identify the atomic parentage of the valence band states. A comparison of the electronic structure of LnBaCo2O5+delta (Ln = Gd, Dy, Dy1-xTbx - Ln-112; 0 smaller or equal to delta smaller or equal to 1) and LnBaCo4O7 (Ln = Yb - Ln-114) single-crystal surfaces is made using synchrotron photoemission spectroscopy. In both cases, the states close to the Fermi energy are found to be of mixed Co 3d/O 2p character, and the comparison allows identification of states due to low spin Co3+ in octahedral environments. The contributions from Ln elements to the valence band are found at higher binding energies.