Self-report measures partially explain consumers’ purchasing choices, which are inextricably linked to cognitive, affective processes and implicit drives. These aspects, which occur outside of awareness and tacitly affect the way consumers make decisions, could be explored by exploiting neuroscientific technology. The study investigates implicit behavioural and neurovascular responses to emotionally arousing and high-engagement advertisements (COVID-19 content). High-engagement advertisements and control stimuli were shown in two experimental sessions that were counterbalanced across participants. During each session, hemodynamic variations were recorded with functional Near-Infrared Spectroscopy (fNIRS) of the prefrontal cortex (PFC), a neurophysiological marker for emotional processing. The implicit association task (IAT) was administered to investigate the implicit attitude. An increase in the concentration of oxygenated haemoglobin (O2Hb) was found for the high-engagement advertising when this category of stimuli was seen first. Specular results were found for deoxygenated haemoglobin (HHb) data. The IAT reported higher values for highly engaging stimuli. Increased activity within the PFC suggests that highly engaging content may be effective in generating emotional arousal and increasing attention when presented before other stimuli, which is consistent with the higher IAT scores, indicating more favourable implicit attitudes. This evidence suggests that the effectiveness of highly engaging advertising-related messages may be constrained by the order of advertisement administration.