There is a thin layer of organic lubricant on commercial silver (Ag) flakes that are widely used as the fillers in electrically conductive adhesives (ECAs). This lubricant layer highly affects the properties such as conductivity of the ECAs. Therefore, understanding the behavior of Ag flake lubricant layer is essential for developing high performance ECAs. This work is aimed at studying the chemical nature of the lubricant layer, interaction between the lubricant layer and Ag flakes, and thermal behavior of the lubricants during heating. A blank Ag powder is ball-milled into Ag flakes with five fatty acids that have different carbon–hydrogen chain length as lubricants. After lubrication, the Ag flakes are studied using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetry (TG), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). It is found that (i) Ag flakes lubricated with fatty acids of different chain lengths have exothermic DSC peaks and mass losses at different temperatures, (ii) the lubricant layer on the lubricated Ag flake surfaces is a salt formed between the acid and Ag, and (iii) exothermic DSC peaks (in air) of a lubricated Ag flake is probably due to the oxidation of lubricant layer on the Ag flake surface.