The emotion generated by the touch of materials is studied via a protocol based on blind assessment of various stimuli. The human emotional reaction felt toward a material is estimated through (i) explicit measurements, using a questionnaire collecting valence and intensity, and (ii) implicit measurements of the activity of the autonomic nervous system, via a pupillometry equipment. A panel of 25 university students (13 women, 12 men), aged from 18 to 27, tested blind twelve materials such as polymers, sandpapers, wood, velvet and fur, randomly ordered. After measuring the initial pupil diameter, taken as a reference, its variation during the tactile exploration was recorded. After each touch, the participants were asked to quantify the emotional value of the material. The results show that the pupil size variation follows the emotional intensity. It is significantly larger during the touch of materials considered as pleasant or unpleasant, than with the touch of neutral materials. Moreover, after a time period of about 0.5 s following the stimulus, the results reveal significant differences between pleasant and unpleasant stimuli, as well as differences according to gender, i.e., higher pupil dilatation of women than men. These results suggest (i) that the autonomic nervous system is initially sensitive to high arousing stimulation, and (ii) that, after a certain period, the pupil size changes according to the cognitive interest induced and the emotional regulation adopted. This research shows the interest of the emotional characterization of materials for product design.