The formation of silver particles as initial catalyst for the electroless copper deposition is an essential part of the formation of conductive structures in flexible electronics. In this work, we have investigated the basic mechanism using the citrate anion for the fixation of silver species and later metal catalyst formation directly on a textile substrates surface. During the particle formation process and the subsequent electroless copper deposition, silver changes its oxidation state several times. While the decomposition of bulk silver citrate leads to silver metal, the distribution on the substrate surface leads to silver oxide due to the oxidation under air. Finally, the reducing conditions in the copper deposition step, i.e. alkaline formaldehyde, convert any silver-ion to silver metal. In parallel, the thermal decomposition of silver citrate also forms CO2 and hexane-2,5-dione. The latter is the result of an auto oxidation reaction similar to Kolbe electrolysis, i.e. symmetrical radical recombination of two acetonyl radicals remaining from the decarboxylated citrate scaffold.