The network of relations between Physical Education (PE) teachers' self-efficacy, goal orientations, attitudes, intentions and behaviours concerning the implementation of a new PE curriculum was examined. Participants were 290 Greek junior high school PE teachers. Two years after the introduction of the new curriculum, participants responded to de-identified questionnaires with acceptable psychometric properties. Mastery-oriented and high self-efficacious teachers had positive attitudes towards the new curriculum, implemented the biggest number of teaching plans and they intended to do the same in the future. Performance approach goal orientation had low positive relationship with the implementation of teaching plans and no relationship with intention to do the same in the future, while performance avoidance goal was not related to any determinant of curriculum implementation and intention. The effects of mastery goal orientation on intention and behaviour were mediated by self-efficacy to achieve an educational aim which is an end in itself, that is, the promotion of students' self-regulation in exercise settings. The effects of performance approach goal orientation on behaviour were mediated by self-efficacy to achieve a curricular goal which is a means to promote other educational aims, that is, the adoption of student-centred teaching styles. Teaching experience was negatively related to implementation of the new curriculum and with most of its determinants. Strategies aiming to strengthen teachers' self-efficacy, mastery goals, attitudes and intentions to implement a new curriculum are suggested. (Contains 3 notes, 1 table, and 3 figures.)