Silver dendrites were obtained on Cu plate by a classic galvanic displacement process. The process of preparing Ag particles was performed at different immersion times in AgNO3 solution, and the best process parameters were selected according to the enhancement effect of the Raman spectra of Rhodamine 6G. Ag-Cu substrates were chosen for a Surface-enhanced Raman scattering (SERS) study of biocomplexes because their preparation is cost effective and simple, and the relative homogeneous signal enhancement on the prepared silver SERS-active substrate was obtained. The rapid process of surface preparation was applied to identify the mode of coordination. Biocomplexes of Co and Ni ions with adenosine triphosphate form in neutral pH were immersed on the Ag dendrites, and SERS spectra of these compounds were collected. This research work was carried out in order to determine different types of coordination in the same pH conditions and relatively low concentration using SERS which is an emerging and promising technique for the determination of coordination types in biocomplexes.