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The Left ventricular ejection time (LVET) is one of the primary surrogates of the left ventricular contractility and stroke volume. Its continuous monitoring is considered to be a valuable hypovolumia prognostic parameter and an important risk predictor in cardiovascular diseases such as cardiac and light chain amyloidosis. In this paper, we present a novel methodology for the assessment of LVET based the Photoplethysmographic (PPG) waveform. We propose the use of Gaussian functions to model both systolic and diastolic phases of the PPG beat and consequently determine the onset and offset of the systolic ejection from the analysis of the systolic phase 3rd derivative. The results achieved by the proposed methodology were compared with the algorithm proposed by Chan et al. , revealing better estimation of LVET (15.84 ± 13.56 ms vs 23.01 ± 14.60 ms), and similar correlation with the echocardiographic reference (0.73 vs 0.75).