In the current study, we examine the role of situation-specific motivational profiles in the effectiveness of video modeling examples for learning problem-solving and self-assessment accuracy in the domain of biology. A sample of 342 secondary school students participated in our study. Latent profile analysis resulted in four motivational profiles: (a) good-quality profile (high autonomous motivation, moderate introjected and external motivation), (b) moderately positive profile (moderate motivation levels with relatively higher autonomous motivation), (c) moderately negative profile (moderate motivation levels with relatively higher external motivation), and (d) poor-quality profile (moderate external, low autonomous motivation). Findings showed students with good-quality or moderately positive profiles learned more from the video modeling in terms of problem-solving and self-assessment accuracy than students with poor-quality or moderately negative profiles. Furthermore, students with a moderately negative profile outperformed students with a poor-quality profile on problem-solving and self-assessment accuracy. Results further indicated that students with good-quality and moderately positive profiles experienced studying the video modeling examples as less effortful than students with poor-quality or moderately negative profiles. Overall, our results demonstrated that knowing about students' motivational profiles could help explain differences in how well students learn problem-solving as well as self-assessment skills from watching video modeling examples.