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Objective: Sympathetic nervous system activity (SNSA) can rapidly modulate arterial stiffness, thus making it an important biomarker for SNSA evaluation. Pulse wave velocity (PWV) is a well-known quantitative indicator of arterial stiffness, but its functional responsivity to SNSA has not been elucidated. This paper reports a method to estimate rapid changes in peripheral arterial stiffness induced by SNSA using local PWV (LPWV) and to further quantify SNSA based on the estimated stiffness. Methods: LPWV was measured from the artery near the wrist to the artery near the forefinger using a biodegradable piezoelectric sensor and a photoplethysmography sensor in an electrocutaneous stimulus experiment in which pain evokes the SNSA. The relationship between LPWV, simultaneously measured peripheral arterial stiffness index, and self-reported pain intensity was quantified. Results: The stiffness estimated by LPWV alone and the stiffness estimated by LPWV and arterial pressure both approximate the peripheral arterial stiffness index (R2 = 0.9775 and 0.9719). Pain intensity can be quantitatively evaluated in a sigmoidal relationship by either the estimated stiffness based on LPWV alone (r = 0.8594) or the estimated stiffness based on LPWV and arterial pressure (r = 0.9738). Conclusion: Our results demonstrated the validity of LPWV in the quantitative evaluation of SNSA and the optionality of blood pressure correction depending on application scenarios. Significance: This study advances the understanding of sympathetic innervation of peripheral arteries through the sympathetic responsivity of LPWV and contributes a quantitative biomarker for SNSA evaluation. [ABSTRACT FROM AUTHOR]