Copper was found to form 1:1 and 1:2 complexes with glycerin at pH values above 12.2. With this solution containing formaldehyde as the reducing agent and bipyrizyl as an additive, electroless copper plating was achieved at the high rate of 7 to 10 μm/h. The stability of the solution was greatly enhanced by controlling the glycerin/Cu molar ratio and by intermittent filtration, but it is still inferior to conventional energy dispersive thermal analysis baths. The kinetics of the self‐decomposition was formulated, considering acceleration due to copper formed during the decomposition. Fairly good agreement was obtained between the data and the values calculated in this manner. The kinetics here can also be applied to other electroless plating systems.