Research consistently shows that teaching behaviour is a highly-important indicator of learning environments. Based on a teacher effectiveness model with six observable teaching behaviour domains (safe learning climate, efficient classroom management, clarity of instruction, activating teaching, teaching–learning strategies, and differentiation), the present paper examines the psychometric quality of the My Teacher questionnaire for capturing student perceptions of teaching behaviour in the Spanish secondary-education context. Additionally, this study validated the model of teaching behaviour and student engagement and its relevance in Spain. 7114 students of 410 teachers attending 56 public and private Spanish schools constituted the sample. The six teaching behavioural dimensions model were confirmed in the Spanish context. Regarding student academic engagement, the presence of two domains (behavioural and emotional engagement) were confirmed. Furthermore, results of a multiple-group structural equation modeling path analysis, examining the relationship between teaching behaviour and student engagement across different teaching experiences, revealed differential effects of teaching behaviour influences on students’ engagement. The percentage of explained variance was larger for emotional engagement than for behavioural engagement. Furthermore, teachers’ teaching experience explained differences in the relationship between perceived teaching behaviour and engagement. Two domains (learning climate and activating teaching) appeared to be the two most-important teaching domains for students’ behavioural engagement while, for emotional engagement, the most important domains for student engagement were learning climate and teaching learning strategies.