Electrophysiological studies have strongly implicated theta-band activity in human working memory processes. Concurrently, work on spontaneous, non-task-related oscillations has revealed the presence of long-range temporal correlations (LRTCs) within sub-bands of the ongoing EEG, and has begun to demonstrate their functional significance. However, few studies have yet assessed the relation of LRTCs (also called scaling relations) to individual differences in cognitive abilities. The present study addressed the intersection of these two literatures by investigating the relation of narrow-band EEG scaling relations to individual differences in working memory ability, with a particular focus on the theta band. Fifty-four healthy adults completed standardized assessments of working memory and separate recordings of their spontaneous, non-task-related EEG. Scaling relations were quantified in each of the five classical EEG frequency bands via the estimation of the Hurst exponent obtained from detrended fluctuation analysis. A multilevel modeling framework was used to characterize the relation of working memory performance to scaling relations as a function of general scalp location in Cartesian space. Overall, results indicated an inverse relationship between both delta and theta scaling relations and working memory ability, which was most prominent at posterior sensors, and was independent of either spatial or individual variability in band-specific power. These findings add to the growing literature demonstrating the relevance of neural LRTCs for understanding brain functioning, and support a construct- and state-dependent view of their functional implications.