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Previous work showed that, when we interact with other people, an alignment of psychophysiological measures occur as a clue about the intensity of the social interaction. Available evidence highlighted increase autonomic synchrony, known as physiological linkage, during intense dyadic situations, like conflictual conversations within romantic couples, friends, or therapeutic settings. Starting from the idea that higher physiological linkage could support better performance and be correlated with approach attitudes (Behavioral Activation System, BAS), in the present study a conflictual situation was proposed by making subjects compete during an attentional task and stressing the importance to win as a measure of future professional success. Autonomic activity (electrodermal: skin conductance level and response: SCL, SCR; and cardiovascular indices: heart rate: HR) was recorded during the task, where subjects received trial-related feedbacks on their performance, and an average score halfway which (fictitiously) assessed their position in terms of accuracy and reaction times with respect to the opponent. In parallel, behavioral inhibition and activation have been assessed by means of the Behavioral Inhibition/Activation System Questionnaire (BIS/BAS). 32 subjects coupled in 16 dyads were recruited. Intra-subject analyses revealed that, after the general evaluation assessing a winning condition, the behavioral performance improved and the electrodermal response increased. Also, correlational analyses showed a relation between BAS, and specifically BAS reward, with SCR. Inter-subject analyses showed higher synchrony in SCR and HR after the feedback. Such results confirm the increased synchronic effect after a highly conflictual condition, and the presence of a relation between subjective performance, approach-related motivations, and physiological linkage.