Construction megaprojects play a significant role in today’s infrastructure provision in terms of sustainable development, and their increasing proliferation worldwide means the environmentally responsible behavior (ERB) of those involved are becoming of vital importance. This study investigates how ERB can be best supported in megaprojects by first identifying the motivational factors that are involved based on the theory of planned behavior (TPB), followed by a survey of 188 managers involved in China megaprojects to test the TPB model using Partial Least Squares Structural Equation Modeling (PLS-SEM). The results strongly support the TPB model’s predictive ability, with subjective norms being the strongest predictors, followed by attitudes and perceived behavioral control. These findings provide support for decision makers in helping to cultivate and improve the level of megaproject ERB in China and many other such countries that are similarly involved.