A soft route for the preparation of catalytically active multilayers of Pt films free from poisoning effects is reported. The SAMs (self-assembled monolayers) were initially formed on the gold substrates and they act as nucleating centers initiating the formation of multilayers of Pt on gold substrates. The nanoscale to mesoscale structures of Pt thus prepared were characterized by SEM and XPS. The SAM-based Pt structures exhibited well-defined hydrogen adsorption, desorption regions associated with very high charge indicating high surface area Pt. The electrocatalytic activity of the multilayers of Pt was characterized by methanol oxidation and a comparison was made with two commercial Pt catalyst preparations.