We report the x-ray absorption study of the single crystal YBaCuFeO5 (YBCFO) to investigate the role of charge, orbital and local structure around the associated Fe/Cu cations on the electrical transport behavior of YBCFO. A resistivity transition is observed ~125K. X-ray linear dichroism (XLD) at Fe L3,2-edge shows different preferential occupation of eg-orbitals below (3d3z2-r2) and above (3dx2-y2) the transition temperature (125K). Larger resistivity along c-axis as compared to the ab-plane is argued in terms of direction dependent hybridization of Fe/Cu 3d - O 2p states as evident by the temperature dependent O K-edge XANES spectra and larger Fe - Oapical bond length compared to Fe - Obasal. Unusual increase in Debye-Waller Factor for Fe at 125K, accompanied by an increase in Fe – O bond distance, is observed, with expected temperature evolution of DWF for Cu. These findings reveal the distortion in square pyramidal sublattice associated with iron square pyramid. Fe/Cu K-edge spectra of YBCFO single crystal reveal the existence of Fe and Cu in Fe3+ and Cu2+ oxidation states, respectively.