Monitoring of cardiovascular function on a beat-to-beat basis is fundamental for protecting patients in different settings including emergency medicine and interventional cardiology, but still faces technical challenges and several limitations. In the present study, we propose a new method for the extraction of cardiovascular performance surrogates from analysis of the photoplethysmographic (PPG) signal alone.We propose using a multi-Gaussian (MG) model consisting of five Gaussian functions to decompose the PPG pulses into its main physiological components. From the analysis of these components, we aim to extract estimators of the left ventricular ejection time, blood pressure and vascular tone changes. Using a multi-derivative analysis of the components related with the systolic ejection, we investigate which are the characteristic points that best define the left ventricular ejection time (LVET). Six LVET estimates were compared with the echocardiographic LVET in a database comprising 68 healthy and cardiovascular diseased volunteers. The best LVET estimate achieved a low absolute error (15.41 ± 13.66 ms), and a high correlation (ρ = 0.78) with the echocardiographic reference.To assess the potential use of the temporal and morphological characteristics of the proposed MG model components as surrogates for blood pressure and vascular tone, six parameters have been investigated: the stiffness index (SI), the T1_d and T1_2 (defined as the time span between the MG model forward and reflected waves), the reflection index (RI), the R1_d and the R1_2 (defined as their amplitude ratio). Their association to reference values of blood pressure and total peripheral resistance was investigated in 43 volunteers exhibiting hemodynamic instability. A good correlation was found between the majority of the extracted and reference parameters, with an exception to R1_2 (amplitude ratio between the main forward wave and the first reflection wave), which correlated low with all the reference parameters. The highest correlation ([Formula: see text] = 0.45) was found between T1_2 and the total peripheral resistance index (TPRI); while in the patients that experienced syncope, the highest agreement ([Formula: see text] = 0.57) was found between SI and systolic blood pressure (SBP) and mean blood pressure (MBP).In conclusion, the presented method for the extraction of surrogates of cardiovascular performance might improve patient monitoring and warrants further investigation.