This paper discussed the moderating role of values-based and agile leadership in the relationship between the psychological characteristics and affective well-being of educators. It employed a mixed-method approach, combining quantitative analysis and qualitative insights. The study emphasized the importance of resilience, adaptability, and ethical leadership in enhancing educators’ well-being and fostering supportive and adaptive teaching environments. The paper employed a mixed-method design, integrating 384 valid survey responses from teachers with qualitative data obtained from 10 administrators. The quantitative data were analysed using SmartPLS software, where Structural Equation Modelling (SEM) was performed to examine the statistical relationships among the variables. The findings highlighted that resilience, adaptability, future expectations, and self-efficacy significantly influenced affective well-being. The results further established that values-based leadership and agile leadership were also integral in ensuring educators’ overall well-being. For the qualitative analysis, insights obtained from semi-structured interviews were transcribed verbatim to identify significant codes, which facilitated the thematic analysis. Six major themes were developed, emphasizing the role of leadership in fostering psychological safety, trust, empowerment, and emotional resilience. The qualitative findings complemented the quantitative results and supported the understanding that agile leadership and values-based practices substantially enhanced educators’ emotional well-being. Furthermore, recommendations, including the implementation of work–life balance policies and adherence to leadership models, were also proposed.