Crystal and electronic structure properties of bimetallic AgAu and AgCu alloy thin films were investigated by X-ray spectroscopic techniques. The aim of this study is to probe the influence of Au or Cu atoms on the electronic behaviors of Ag ions in bimetallic alloy materials that yields different crystal properties. To identify the mechanisms causing crystal phase transitions, study were supported by the collected EXAFS (Extended X-ray Absorption Fine Structure) data. Crystal structures of both Cu and Au doped bimetallic Ag samples were determined mainly in cubic geometry with "Fm3m" space group. Through the Ag-Au and Ag-Cu molecular interactions during bimetallic alloy formations, highly overlapped electronic levels that supports large molecular band formations were observed with different ionization states. Besides, traces of the d-d interactions in Au rich samples were determined as the main interplay in the broad molecular bond formations. The exact atomic locations and types in the samples were determined by EXAFS studies and supported by the performed calculations with FEET scientific code. (C) 2016 Elsevier B.V. All rights reserved.