Strategic management research (SMR) has provided some of the main theoretical foundations to the study of academic spin-offs (ASO). The influence of SMR's rooted conception of firm performance as resulting from the structure-and-agency duality is clear on this nascent field's specialized literature. Nevertheless, specific characteristics of agency, of structure and of their interplay during ASO creation are still under-researched though potentially relevant to understand and explain spin-offs' heterogeneity. Thus, this paper presents a cognitive approach used to characterize this duality in the spin-off process, as perceived by entrepreneurs. Reported findings are the first results of the initial case study of an on-going multiple-case comparative research. This initial investigation is being conducted in an embryonic Brazilian high-technology academic spin-off focused on developing products from carbon nanotubes to various industrial applications, such as fuel cells, supercapacitors and batteries. A hybrid version of cognitive mapping and retrospective roadmapping was used as a data collection and modeling technique. Envisaging theory development, evidence-based propositions were derived from results in order to be further investigated by future works. Though partial, these initial findings and the way they were obtained may already represent a theoretical and methodological contribution to the advancement of this technology management research strand.