Defined topographic features may be produced on the workpiece surface of difficult-to-machine materials through the pulse electrochemical machining (PECM). Due to the contactless feature of PECM, mechanical influences, and their side effects become ignorable. In this study, a picosecond laser, which induces little thermal impact, was applied to micromachine the cathode of PECM with groove patterns, and replication of the patterns on the anode of PECM was carried out using an industrial PECM installation. The results of the case study show that the picosecond laser achieved high machining precision (<6.5% to the target size) with excellent surface integrity on the cathode of PECM, and the groove patterns were successfully replicated on the anode of PECM, although deviations of certain geometric parameters were detected between the two PECM electrodes. These deviations may result from the rounding and widening effects during the PECM processing.