Already in 2016, the German educational policy adopted the Education in the Digital World strategy, recommending that all teachers should become experts in using media. However, despite this initiative regarding the promotion of innovative forms of teaching using digital media, most teachers did not feel optimally prepared to successfully cope with the demands of implementing e-learning during the COVID-19 pandemic. Most empirical studies on potential barriers to innovation pertain to comparatively easy, changeable environmental factors, whereas only a few studies have focused on teachers as an individual factor so far. Since several organizational psychological studies on the relationships between innovativeness and personality traits in professional contexts identified the personality trait of openness to experience to be particularly influential on the innovative behaviors of employees’, our study aimed to explore whether comparable results can also be found in the educational context. Therefore, we conducted a cross-sectional survey (n = 201) to analyze to what extent the Big Five personality traits are related to pre-service teachers’ self-concept of professional knowledge and, in particular, its digitalization-related domains. The results of our canonical correlation analysis show that the two personality traits of openness to experience and conscientiousness appear to be significantly related to the overall professional knowledge of our sample. Furthermore, a dominant affinity for technology seems to be associable with the risk of lower values on personality traits that are regarded to be pedagogically relevant. However, we found that our canonical model could also get along with fewer variables since the actual digitalization-related teaching skills were not sufficiently reflected by the canonical solution but were rather caught up in the domain of pedagogical content knowledge. Interpretations of these findings as well as practical implications are discussed.