Pulse waves continuously change with respect to the characteristics and status of the cardiovascular system and in relation to the blood pressure (BP) and the pulse wave velocity (PWV). Monitoring the vascular condition by analyzing the variations in pulse waveforms has been used to diagnose vascular disorders and in drug treatment of arteriosclerosis and peripheral circulatory obstruction. In this paper, we investigated the vascular characteristic index with regard to the BP and classified by pulse wave signals. The pressure pulse wave and photoplethysmography (PPG) were measured simultaneously while subjects exercised, producing changes in the BP, to analyze the variation in the vascular characteristic index. We investigated the correlation between the BP and vascular characteristic index with regard to the classification methods of the pulse wave. The reflection index (RI) and vascular stiffness index were correlated with the diastolic BP, but no correlation was found between these parameters and the systolic BP. These results suggest the possibility of estimating BP through simple measurements of pulse waves.