Facial expressions are in reaction to basic tastes by the response to receptor stimulation. The objective of this study was to assess the autonomic nervous system responses to basic tastes in chocolates and to identify relationships between conscious and unconscious responses from participants. Panelists (n = 45) tasted five chocolates with either salt, citric acid, sugar, or monosodium glutamate, which generated four distinctive basic tastes plus bitter, using dark chocolate. An integrated camera system, coupled with the Bio-Sensory application, was used to capture infrared thermal images, videos, and sensory responses. Outputs were used to assess skin temperature (ST), facial expressions, and heart rate (HR) as physiological responses. Sensory responses and emotions elicited during the chocolate tasting were evaluated using the application. Results showed that the most liked was sweet chocolate (9.01), while the least liked was salty chocolate (3.61). There were significant differences for overall liking (p < 0.05) but none for HR (p = 0.75) and ST (p = 0.27). Sweet chocolate was inversely associated with angry, and salty chocolate positively associated with sad. Positive emotion-terms were associated with sweet samples and liking in self-reported responses. Findings of this study may be used to assess novel tastes of chocolate in the industry based on conscious and emotional responses more objectively.