Deficient cognitive control (CC) over emotional distraction is a central characteristic of borderline personality disorder (BPD). Reduced activation of the left dorsolateral prefrontal cortex (dlPFC) has been linked to this deficit. This study investigates whether it is possible to ameliorate CC deficits via anodal tDCS over the left dlPFC in BPD. Furthermore, we investigate whether the extent of CC impairment influences how well one responds to tDCS. The effect of a single-session tDCS (1 mA for 20 min, reference electrode on the contralateral mastoid bone) to the left dlPFC (F3) on the CC of patients with BPD (N = 20) and healthy control participants (HCs, N = 20) was examined in a double-blinded, balanced randomized, sham-controlled crossover trial. A delayed response working memory task with negative, neutral and positive pictures presented during the delay period was conducted to assess CC. Stimulation was applied simultaneously with the task. Negative pictures caused prolonged response times as compared to a control condition in patients with BPD and HCs. Anodal tDCS to the left dlPFC did not significantly reduce this interference effect in the overall sample. Further analyses showed, however, that participants with impaired CC profited the most from anodal tDCS. In the subgroup of participants who actually showed an interference effect we found the expected significant amelioration of CC under tDCS. The present study demonstrates that anodal tDCS applied to the left dlPFC improves deficient CC. Thereby, base-level performance moderates tDCS effects. Hence, tDCS might be suitable to support behavioral trainings to enhance CC specifically in people whose impairments in CC are comparably high.