The oil‐pressboard insulation on the valve side of the converter transformer withstands pulsating square wave voltage. The voltage contains lots of DC components and high‐order harmonics, which is likely to cause insulation failures. The partial discharge and space charge experiments of oil‐impregnated pressboard under DC superimposed harmonic voltage are conducted to study the effects of harmonic frequency and DC components on the discharge and charge accumulation and to explore the correlation mechanism of charge dynamic behaviour and discharge. Firstly, it is found that high‐order harmonic voltage promotes the partial discharge generation, but DC component suppresses the discharge. Moreover, the charge inside the pressboard is mainly injected in the same polarity and accumulates over time. The space charge density near the electrode increases with the increase of harmonic frequency, and the large amount of charge injection leads to electric field distortion. Meanwhile, the electric field direction changes faster, and the frequent charge injection and extraction behaviours make the charge recombination intensify, which promotes the discharge. Through the above analysis, the influence law of harmonic voltage on the failure of oil‐pressboard insulation is obtained, providing a theoretical basis for the structural optimisation and condition assessment of the converter transformer insulation.