<p>The development of innovative work behavior is a prerequisite for achieving the adoption and promotion of new ideas that benefit the organization. This study investigates personal traits that are associated with innovative work behavior of teachers in early childhood education, and specifically irrational beliefs and burnout. Their roles were assigned based on Job Demands-Resources Theory, and they were analyzed by employing structural equation modeling. Data was taken for the participation of early childhood education teachers (<i>N</i> = 378) via self-reported questionnaires in Greece. The proposed model exhibited a satisfactory goodness-of-fit to the empirical data, highlighting the effects on innovative work behavior and contributing to the expansion of the utilized theory. Personal resources affected negatively teachers’ disengagement, while personal demands influenced their exhaustion positively. Furthermore, burnout’s dimensions seemed to have different impact on innovative work behavior. The findings are interpretable in the context of modern theories, while a discussion on theoretical and practical implications along with emerging ideas and perspectives for further research is provided.</p>