The capacity for transcranial direct current stimulation (tDCS) to increase learning and cognition shows promise for the development of enhanced therapeutic interventions. One potential application is the combination of tDCS with cognitive training (CT), a psychological intervention which aims to improve targeted cognitive abilities. We have previously shown that tDCS enhanced performance accuracy, but not skill acquisition, on a dual n-back working memory (WM) CT task over repeated sessions. In the current study, we investigated the optimal timing for combining tDCS with the same CT task to enhance within and between session performance outcomes across two daily CT sessions. Twenty healthy participants received in a randomised order 30 min of anodal tDCS to the left dorsolateral prefrontal cortex immediately before (‘offline’ tDCS) and during performance (‘online’ tDCS) on a dual n-back WM CT task, in an intra-individual crossover design. Analyses examined within and between session consolidation effects of tDCS on CT performance outcomes. Results showed that ‘online’ tDCS was associated with better within session skill acquisition on the CT task, with a significant difference found between conditions the following day. These results suggest that ‘online’ tDCS is superior to ‘offline’ tDCS for enhancing skill acquisition when combining anodal tDCS with CT. This finding may assist with the development of enhanced protocols involving the combination of tDCS with CT and other rehabilitation protocols.