The renewable mercury film electrode, applied for the determination of titanium(IV) ultratraces using differential pulse catalytic adsorptive cathodic stripping voltammetry (DP CAdSV) in the presence of mandelic acid as a ligand and chlorate(V) as an oxidant is represented. The calibration graph obtained for Ti(IV) is linear from 0.05 nM (2.39 ng L−1) to 95 nM (4.55 µg L−1) for a preconcentration time of 30 s, with correlation coefficient of 0.9995. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 8.6 mm2 the detection limit for a preconcentration time of 180 s is as low as 0.006 nM (0.29 ng L−1). The repeatability of the method at a concentration level of the analyte as low as 23.9 ng L−1, expressed as RSD is 1.8 % (n=5). The proposed method was successfully applied and validated by studying the certified reference material NWTM‐26.3 and simultaneously recovery of Ti(IV) from spiked samples.