Pulse wave velocity (PWV) is a marker of arterial stiffness and may permit continuous, non-invasive, and cuff-less monitoring of blood pressure. Here, robust PWV estimation was sought by application of system identification to proximal and distal arterial waveforms. In this approach, the system that optimally couples the proximal waveform to the distal waveform is identified, and the time delay of this system is then used to calculate PWV. To demonstrate proof-of-concept, a standard identification technique was applied to non-invasive impedance cardiography and peripheral arterial blood pressure waveforms from six humans subjected to progressive reductions in central blood volume induced by lower body negative pressure. This technique estimated diastolic pressure with an overall root-mean-squared-error of 5.2 mmHg. For comparison, the conventional detection method for estimating PWV yielded a corresponding error of 8.3 mmHg.