This study explored the dimensionality and measurement invariance of a multidimensional measure for evaluating teachers’ perceptions of the quality of their relationships with principals at the dyadic level. Participants were 630 teachers (85.9% female) from 220 primary and 204 secondary schools across the Netherlands. Teachers completed the 10-item Principal–Teacher Relationship Scale (PTRS) for their principals. Confirmatory factor analyses (CFA) provided evidence for a two-factor model, including a relational Closeness and Conflict dimension. Additionally, multigroup CFA results indicated strong invariance of the PTRS across school type, teacher gender, and teaching experience. Last, secondary school teachers and highly experienced teachers reported lower levels of Closeness and higher levels of Conflict in the relationship with their principal compared to primary school teachers and colleagues with less experience. Accordingly, the PTRS can be considered a valid and reliable measure that adds to the methodological repertoire of educational leadership research by focusing on both positive and negative aspects of dyadic principal–teacher relationships.