This study aims to analyse the relationship between students' mathematics achievement in Programme for International Student Assessment (PISA) 2012 and the instructional climate-related factors in the index of principals' perceptions (learning hindrance, teacher morale and teacher intention). As preliminary analysis procedure, the chi-squared automatic interaction detection analysis was performed with relevant independent variables. Teacher's achievement expectation from students and achievement-oriented behaviours were other significant predictive indicators on PISA mathematics achievement. Based upon these independent variables and standard deviation estimates of PISA mathematics scores, the present research developed a theoretical model by means of confirmatory factor analysis, explaining how students' PISA mathematics achievement is associated with classroom and within school homogeneity through teachers' expectation and achievement-oriented behaviours. Results showed that the developed model provided a great model-data fit. This model revealed that classroom achievement homogeneity and within school achievement homogeneity were the most important predictors on students' PISA mathematics achievement.