The aim was to implement a value-promoting programme (Teaching Personal and Social Responsibility, TPSR) and to assess its impact on psychological and contextual variables in students comparing the differences among one group that applied it in several subjects, another group only in Physical Education (PE), and a control group. Method: The programme was applied for eight months with 257 students from three secondary school centres (151 boys and 106 girls) with a mean age of 15.97 years (SD = 2.31). They were in three groups: one group with 67 students (control group), one group with 90 students receiving at least 60% of the total teaching time using the value-promoting programme (experimental group for global education, EG-GE), and one group with 100 students (experimental group for physical education only, EG-PE). The main improvements in the results were found in the EG-GE for responsibility, psychological mediator index, self-determination index, resilience, climate, and prosocial behaviour. In the EG-PE, improved results were observed in the self-determination index, classroom climate, and prosocial behaviour. Female and EG-GE students improved much more than male and EG-PE students. The outcomes in psychological variables can be higher if TPSR is applied to the whole subjects apart from physical education. These results are even more pronounced for female students in personal and social responsibility. It is worth highlighting the importance of coordinating educational institutions to facilitate the involvement of the greatest number of teachers.