Neurofeedback (NFB) training with brain-computer interfaces (BCIs) is currently being studied in a variety of neurological and neuropsychiatric conditions in an aim to reduce disorder-specific symptoms. For this purpose, a range of classification algorithms has been explored to identify different brain states. These neural states, e.g., self-regulated brain activity vs. rest, are separated by setting a threshold parameter. Measures such as the maximum classification accuracy (CA) have been introduced to evaluate the performance of these algorithms. Interestingly enough, precisely these measures are often used to estimate the subject’s ability to perform brain self-regulation. This is surprising, given that the goal of improving the tool that differentiates between brain states is different from the aim of optimizing NFB for the subject performing brain self-regulation. For the latter, knowledge about mental resources and work load is essential in order to adapt the difficulty of the intervention accordingly. In this context, we apply an analytical method and provide empirical data to determine the zone of proximal development (ZPD) as a measure of a subject’s cognitive resources and the instructional efficacy of NFB. This approach is based on a reconsideration of item-response theory (IRT) and cognitive load theory for instructional design, and combines them with the CA curve to provide a measure of BCI performance.