Functional near-infrared spectroscopy (fNIRS) is an optical imaging technique measuring relative hemodynamic changes in superficial cortical structures. It has successfully been applied to detect a hemodynamic response in the somatosensory cortex evoked by irritating mechanical, electrical, and heat stimulations of limbs or the face. The aim of the current study was to explore the feasibility of fNIRS to detect respective responses evoked by irritating chemical stimulations of the nasal divisions of the trigeminal nerve. In two experiments, healthy subjects were exposed to acetic acid and ethyl acetate presented using a respiration-synchronized olfactometer. Results demonstrated that fNIRS can detect a signal in both hemispheres after birhinal (experiment 1: n = 14) and monorhinal (experiment 2: n = 12) stimulations using acetic acid but not ethyl acetate. This is a first evidence that fNIRS might be a suitable imaging technique to assess chemosensory neuronal correlates in the somatosensory cortex thereby offering a new, portable method to evaluate the irritating properties of certain volatiles in an objective, nonverbal, easy, and comparably inexpensive manner.