Acute mental stress is an everyday phenomenon that has evidently intensified over the past decades and poses significant health risks. Conventional methods for stress assessment are not suitable for everyday use. They are suitable only for clinical and laboratory assessment because they require full attention, limit the freedom of movement (sensors, cables), often require trained personnel or special equipment, and thus are cost-intensive. This work investigates camera-based photoplethysmography (cbPPG), a non-contact technique for the monitoring of cardiovascular vital signs, as an alternative for the assessment of acute mental stress that is suitable for everyday use. As a non-contact technique cbPPG is considered susceptible to artifacts. To overcome limitations of existing cbPPG methods, this work covers essential developments for the robust extraction of non-contact vital signs in addition to the assessment of acute mental stress. An experimental study was designed and conducted with 65 healthy participants to gain a database for cbPPG including synchronized reference measurements (e.g. electrocardiography, skin conductance, salivary cortisol concentration). The experimental study resulted in the „Dresden Multimodal Biosignal Dataset for the Mannheim Multi-component Stress Test“ (DMBD). In addition, the „Binghamton-Pittsburgh-RPI Multimodal Spontaneous Emotion Database“ (BP4D+) was utilized. For robust extraction of non-contact vital signs measured with cbPPG, a novel method for the extraction of cbPPG signals was developed: O3C. O3C optimizes the combination of the color channels of RGB cameras with an evaluation metric in a specialized, systematic grid search. Several investigations on properties of the novel method revealed that the grid search always identified a global optimum. O3C was independent of different skin tones and the choice of evaluation metric. Temporal normalization of the RGB color channels improved the transferability of O3C between datasets (DMBD, BP4D+). At the example of breath rate measurement, it was shown that the method behind O3C is transferable from pulse rate to other vital signs. In addition, a novel method for automatic, reference-free identification of erroneous measurements was developed on the basis of signal quality indexes (SQIs). The developments on robust extraction of non-contact vital signs contribute to the fundamentals of cardiovascular monitoring that is suitable for everyday use. Among other aspects, this forms the basis for non-contact assessment of acute mental stress with cbPPG. In the experimental study (DMBD), conventional reference methods showed distinct changes in psychometric variables, chemical biomarkers, and contact-based vital signs during acute mental stress. The results are widely in line with existing literature and indicated successful activation of the hypothalamic-pituitary-adrenal axis (HPA axis) as well as sympathetic activation of the autonomic nervous system. A special characteristic of this investigation on stress assessment resides in the large variety of synchronized reference parameters, which allows a side-by-side comparison of the effectiveness of different measurement techniques. To assess the physiological reaction to acute mental stress with non-contact technique, ten vital signs derived with cbPPG were analyzed. The cbPPG vital signs registered positive chronotropy, peripheral vasoconstriction, and altered respiration in accordance with reference measurements. Thus, they also successfully indicated sympathetic activation of the autonomic nervous system. In a machine learning approach, the cbPPG vital signs were effective in detecting the immediate stress response with a fairly high temporal resolution of 30 s. These investigations are unique in terms of their extent and the possibility to adduce diverse synchronized reference measurements for comparison. They provide valuable insights into capabilities and effectiveness of cbPPG for non-contact assessment of acute mental stress. The findings of this work pave the way for robust non-contact monitoring with cbPPG. At the example of acute mental stress, a method for physiological assessment of the human state that is suitable for everyday use has been presented. This provides new opportunities to make use of the great potential that cbPPG offers for numerous everyday applications (e.g. telemedical video consultations, adaptive human-machine interfaces).