The study explores the hormonal influences on entrepreneurial opportunity persuasion decisions (OPD). It also analyzes how behavioural psychology influences the entrepreneurial opportunity recognition-refinement process (OPRR). The machine learning and structural equation modelling analyses of the data from 271 Indian entrepreneurs support the hypotheses of a direct effect of the physiological biomarker—Testosterone-Cortisol Ratio (TCR) and behavioural marker—communities of inquiry (COI) on OPD. Further, partial mediation indicated an indirect positive effect of COI on OPD, with OPRR moderating this relationship. Shedding new light on the enigmatic entrepreneurial opportunity behaviour from a biological and behavioural perspective improves the causal inference of external and socially-influenced COI and internally-triggered TCR. Finally, theoretical and methodological contributions are discussed along with implications that can guide future research on entrepreneurial opportunity behaviours.