Pedagogical content knowledge (PCK) and content knowledge (CK) are key components of teacher competence that affect student progress. However, little is known about how teacher education affects the development of CK and PCK. To address this question, our research group constructed tests to directly assess mathematics teachers’ CK and PCK. Based on these tests, we compared the PCK and CK of four groups of mathematics teachers at different points in their teaching careers in Germany. Confirmatory factor analyses showed that PCK and CK measurement was satisfactorily invariant across the teacher populations considered. As expected, the largest differences in CK and PCK were found between the beginning and the end of initial teacher education. Differences in the structures of teacher education were reasonably well reflected in participants’ CK and PCK.