Abstract The effect of pH and time of heating on formation of palladium porphyrinato complex was investigated and procedure for sample preparation was proposed. Capillary zone electrophoresis method for Pd determination in the form of its porphyrinato complex was developed, where pH of background electrolyte, separation voltage and injection time were optimized. Detection limit equal to 0.8 μg l −1 of Pd was achieved. Other platinum group metals and other heavy metal ions do not interfere with Pd determination. Using the method developed an analysis of a palladium asbestos sample was carried out and compared with that of inductively coupled plasma atomic emission spectrometry.