Sleep quality (SQ) is a crucial aspect of overall health. Poor sleep quality may cause cognitive impairment, mood disturbances, and an increased risk of chronic diseases. Therefore, assessing sleep quality helps identify individuals at risk and develop effective interventions. SQ has been demonstrated to affect heart rate variability (HRV) and skin temperature even during wakefulness. In this perspective, using wearables and contactless technologies to continuously monitor HR and skin temperature is highly suited for assessing objective SQ. However, studies modeling the relationship linking HRV and skin temperature metrics evaluated during wakefulness to predict SQ are lacking. This study aims to develop machine learning models based on HRV and skin temperature that estimate SQ as assessed by the Pittsburgh Sleep Quality Index (PSQI). HRV was measured with a wearable sensor, and facial skin temperature was measured by infrared thermal imaging. Classification models based on unimodal and multimodal HRV and skin temperature were developed. A Support Vector Machine applied to multimodal HRV and skin temperature delivered the best classification accuracy, 83.4%. This study can pave the way for the employment of wearable and contactless technologies to monitor SQ for ergonomic applications. The proposed method significantly advances the field by achieving a higher classification accuracy than existing state-of-the-art methods. Our multimodal approach leverages the synergistic effects of HRV and skin temperature metrics, thus providing a more comprehensive assessment of SQ. Quantitative performance indicators, such as the 83.4% classification accuracy, underscore the robustness and potential of our method in accurately predicting sleep quality using non-intrusive measurements taken during wakefulness.