The organic/metal interface formed upon adsorption of cobalt(II) phthalocyanine (CoPc) molecules on a flat Ag(111) single crystal was investigated using a combination of scanning tunneling microscopy (STM) and photoemission spectroscopy (PES). A flat-lying molecular adsorption with the π conjugated phthalocyanine ligand parallel to the substrate was found to lead to an effective molecule-substrate coupling which governs a template-guided molecular growth. A voltage polarity dependence at the cobalt ion site was emphasized and correlated with the Co 2p core level spectra evolution which sustains an interface-confined reduction effect of the cobalt oxidation state. The formation of interface dipoles was observed via monitoring the changes in the work function (WF) upon deposition. The observations are discussed on the basis of a site-dependent donation/backdonation charge transfer at the molecule-substrate interface.