Arterial stiffness, resulting in loss of the elastic properties of arteries walls, is an indicator of cardiovascular risk, though the presence of disease is not clinically evident. Augmentation index is an important biomarker of arterial stiffness by which the cardiac risk of the patient can be diagnosed. The current paper outlines the non-invasive assessment of arterial stiffness by analyzing the morphology or contour of PhotoPlethysmoGraph (PPG) signal. PPG pulse was optically acquired with the developed photometric measurement device and the desired features were extracted to determine PPG augmentation Index (PAI) through advanced signal processing implemented in MATLAB. PAI was quantified by the fourth derivative of the signal by enhancing the location of inflection point (augmentation point) after conditioning the signal by efficient pre-processing and filtering techniques. The results reveal that the statistical distribution of PAI for healthy subjects presents a very low value and a very tight distribution. On the contrary, patients have a higher value of PAI and a wide asymmetrical shape of distribution. This work also establishes the usefulness of PPG contour analysis in the investigation of changes in the elastic properties of the vascular system. In conclusion, PAI has revealed to be a non-invasive indicator for arterial stiffness assessments. © 2015 National Taiwan University.