Spontaneous blinking is a non-invasive indicator known to reflect dopaminergic influence over frontal cortex and attention allocation in perceptual tasks. 38 participants watched eighteen short film clips (2 min), designed to elicit specific affective states, and arranged in six different emotional categories, while their eye movements were recorded from the vertical electroculogram. The largest blink rate inhibition, reflecting greater attention allocation to the movie, was observed during the presentation of Erotic clips, excerpts on wilderness depicting beautiful landscapes (Scenery), as well as clips showing crying characters (Compassion). Instead, the minimum blink rate inhibition was found for Fear clips, which induced a defensive response with stimulus rejection. Blink rate across time evidenced how Compassion clips elicited early inhibition while Sadness clips induced a slower, later inhibition. Correlation analyses also revealed a negative correlation (r < -0.40) between total blink rate recorded during Erotic and Compassion clips and self-reported interest. Overall, the main variable explaining blink rate was emotional Valence. Results suggest that blink modulation is related with the motivational relevance and biological significance of the stimuli, tracking their differential recruitment of attentional resources. Furthermore, they provide a solid background for studying the emotion-attention patterns and their deficits also in clinical samples (e.g., neurological and psychiatric patients) using spontaneous blinking as a not-interfering psychophysiological measure.