Working memory (WM) is a cognitive system allowing short-term maintenance and processing of information. Maintaining information in WM consists, classically, in rehearsing or refreshing it. Chunking could also be considered as a maintenance mechanism. However, in the literature, it is more often used to explain performance than explicitly investigated within WM paradigms. Hence, the aim of the present paper was (1) to strengthen the experimental dialogue between WM and chunking, by studying the effect of acronyms in a computer-paced complex span task paradigm and (2) to formalize explicitly this dialogue within a computational model. Young adults performed a WM complex span task in which they had to maintain series of 7 letters for further recall while performing a concurrent location judgment task. The series to be remembered were either random strings of letters or strings containing a 3-letter acronym that appeared in position 1, 3, or 5 in the series. Together, the data and simulations provide a better understanding of the maintenance mechanisms taking place in WM and its interplay with long-term memory. Indeed, the behavioral WM performance lends evidence to the functional characteristics of chunking that seems to be, especially in a WM complex span task, an attentional time-based mechanism that certainly enhances WM performance but also competes with other processes at hand in WM. Computational simulations support and delineate such a conception by showing that searching for a chunk in long-term memory involves attentionally demanding subprocesses that essentially take place during the encoding phases of the task.