In the education context, a small number of studies dealt with the effect of teachers’ attitudes on behavioral intentions toward the curriculum change in its implementation stage by the mediating role of their perceived behavioral control. Hence, this study specifically focuses on understanding the effects of mediating variables on the relationship between primary teachers’ attitudes and behavioral intentions toward implementing the new curriculum. The study investigated 627 primary teachers in Myanmar’s government schools in the region of Naypyitaw Union Territory located in the central part of Myanmar, during the academic year 2021-2022 using teachers’ attitudes questionnaire, behavioral intentions questionnaire, and perceived behavioral control questionnaire. Results revealed that teachers had positive attitudes and supportive behavioral intentions toward implementing the new curriculum. The findings also showed teachers’ attitudes had a significant positive predictive effect on their behavioral intentions (r = 0.5, p < 0.01). Moreover, perceived behavioral control had a partially mediating effect between teachers’ attitudes and behavioral intentions toward implementing the new curriculum. In the implementation stage of the new curriculum, the finding revealed the importance of teachers’ perceptions of behavioral control in enhancing their actual new curriculum implementation behavior. It also provided additional empirical evidence in the educational context and also for the policy-makers in education.