Food neophobia, i.e., the aversion to novel foods, and olfaction are both factors strongly affecting food choices. Mounting evidence suggests a higher arousal towards food as a key factor underlying the reluctance to eat what is unfamiliar to us. As the role of olfaction behind this phenomenon is poorly understood, we explored the associations between food neophobia and trait anxiety, olfactory functions (odor threshold, discrimination and identification) and retronasal aroma release from a reference food in a healthy cohort of 83 adult volunteers. We grouped participants in Low-Neophobics or neophilics (n = 35), Medium-Neophobics (n = 32) and High-Neophobics (n = 16) according to the widely recognized Food Neophobia Scale. Participants with higher neophobic tendencies were found to have marginally higher trait anxiety levels than neophilics (p = 0.10). A lower global olfactory functioning and odor discrimination abilities characterized High-Neophobics, while Medium-Neophobics showed a higher odor sensitiveness than Low-Neophobics. Lastly, High-Neophobics showed a lower extent of retronasal aroma release, likely due to a shorter duration of oral processing and higher anxiety-related physiological responses (such as breathing rate). In summary, this study supports the assumption that the conflicting relationship that neophobics have with food may be led by higher levels of arousal toward foods, rather than different chemosensory functions.