The effect of organic additives, polyethylene glycol (PEG), on the trivalent chromium electroplating was analysed in the view point of current efficiency, solution stability and metallurgical structure. It was measured that PEG-containing trivalent chromium solution had about 10% higher current efficiency than pure solution and controlled the micro-crack density of electrodeposits. PEG exhibited profound effect on the solution stability by reducing the consumption rate of formic acid which acts as a complexant to lower the activation energy required for electrochemical reduction of trivalent chromium ions. It was also revealed that the formation of chromium carbide layer was facilitated in the presence of polyethylene glycol, which meant easier electrochemical codeposition of chromium and carbon, not single chromium deposition. Trivalent chromium layer formed from PEG-containing solution was amorphous with local nano-crystalline particles, which were prominently developed on the entire surface after non-oxidative heat treatment.