A novel catalytic adsorptive stripping chronopotentiometric (CC‐CAdSCP) procedure for the determination of Co(II) traces was developed using a lead film electrode (PbFE). The PbFE was generated in situ on a glassy carbon support from a 0.1 M ammonia buffer containing 1×10−5 M Pb(II), 6.5×10−5 M DMG and the target metals. An addition of 0.2 M NaBrO3 to the solution yielded an 11‐fold catalytic enhancement of chronopotentiometric response of the Co(II)‐DMG complex. The CC‐CAdSCP curves were well‐developed, sharp and reproducible (RSD 5.0 % for 5×10−9 M Co(II)). The limit of detection for Co(II) for 210 s of accumulation time was 4×10−10 M (0.024 µg L−1). In addition, the elaborated method allowed the simultaneous quantification of Co(II) and Ni(II) simultaneously.