Background: The insertion of fixed orthodontic appliances increases the risk of dental caries, particularly in adolescents. Caries can be prevented through good oral health behavior. To support adolescents with fixed orthodontic appliances and for promoting oral health behavior, we developed a theory- and evidence-based mHealth program, the WhiteTeeth app. Objective: The objective of our paper was to describe the systematic development and content of the WhiteTeeth app. Methods: For systematic development of the program, we used the intervention mapping (IM) approach. In this paper, we present the results of applying the first 5 steps of IM to the design of an mHealth program: (1) identifying target behaviors and determinants through problem analysis, including a literature search, a survey study, and semistructured interviews, to explore adolescent oral health behavior during orthodontic therapy; (2) defining program outcomes and objectives; (3) selecting theoretical methods and translating them into practical strategies for the program design; (4) producing the program, including a pilot test with 28 adolescents testing the acceptability and usability of the WhiteTeeth app; and (5) planning implementation and adoption. Results: On the basis of our literature search, we identified fluoride use and control of dental plaque levels (eg, tooth brushing and proxy brush usage) as target behaviors for preventing caries. Next, we identified important and changeable determinants of oral health behavior that fitted the theoretical concepts of the Health Action Process Approach (HAPA) theory. The HAPA theory, the self-regulation theory, and the results of the semistructured interviews were used to define the program objectives, that is, the performance and change objectives. After defining the objectives, we identified multiple behavior change techniques that could be used to achieve these objectives, such as providing oral health information and feedback, prompting self-monitoring, coaching of set actions and coping plans, and sending reminders. We translated these methods into practical strategies, such as videos and a brushing timer. Next, we combined these strategies into a single program resulting in the WhiteTeeth app (which is available on both iTunes and Google Play stores as “Witgebit”). Adolescents with fixed orthodontic appliances and dental professionals were included in the development process to increase the success of implementation. The pilot test revealed that the app users appreciated and liked the app. The WhiteTeeth app can be integrated into current orthodontic care. Conclusions: IM allowed us to identify multiple techniques that have been shown to be the most effective in initiating behavior change, but have not yet been incorporated into existing orthodontic apps. The WhiteTeeth app contains all these techniques, which makes it a unique and promising home-based app for promoting oral health in adolescents with fixed orthodontic appliances.