Association of cognitive deficits and diabetic peripheral neuropathy (DPN) is frequent. Working memory (WM) deficits result in impairment of daily activities, diminished functionality, and treatment compliance. Mounting evidence suggests that transcranial Direct Current Stimulation (tDCS) with concurrent working memory training (WMT) ameliorates cognitive deficits. Emboldening results of tDCS were shown in DPN. The study aimed to evaluate the efficacy of anodal tDCS over the left dorsolateral prefrontal cortex (DLPFC) coupled with cathodal right DLPFC with concurrent WMT in DPN for the first time. The present randomized triple-blind parallel-group sham-controlled study evaluated the efficacy of 5 sessions of tDCS over the DLPFC concurrent with WMT in 28 individuals with painful DPN on cognitive (primary) and pain-related, psychiatric outcome measures before, immediately after, and 1-month after treatment protocol. tDCS enhanced the efficacy of WMT on working memory and yielded lower anxiety levels than sham tDCS but efficacy was not superior to sham on other cognitive domains, pain severity, quality of life, and depression. tDCS with concurrent WMT enhanced WM and ameliorated anxiety in DPN without affecting other cognitive and pain-related outcomes. Further research scrutinizing the short/long-term efficacy with larger samples is accredited.