Curiosity and academic self-concept as psychological constructs are often mentioned in education and psychology. These constructs are elusive in terms of how they are exhibited or portrayed and measured. Despite their elusive nature, they are highly significant to the success or otherwise of learners. Therefore, the current study explored curiosity and academic self-concept among students of category "A" Senior High schools in the Central Region of Ghana. Using a descriptive-quantitative method, a sample of 400 students was selected through proportionate-stratified and systematic sampling techniques. Adapted curiosity (Kashdan et al., 2018) and academic self-concept (Liu & Wang, 2005) scales were used for the data collection. The data collected were analysed using frequencies, percentages, and structural equation modelling (SEM). The study revealed that the majority of the students possessed low curious abilities and low academic self-concepts. The study further revealed that curiosity of deprivation sensitivity (b=0.577, p<0.001), the curiosity of stress tolerance (b=0.248, p=0.007), and curiosity of thrill-seeking (b=0.544, p<0.001) positively and significantly predicted academic self-concept of students but the curiosity of joyful exploration and social curiosity did not predict academic self-concept of students. It was concluded that students' curious abilities were precursors to their academic self-concept. Thereupon, teachers need to devise new approaches by allowing students to engage in other learning opportunities without much restrictions so that they could hone their natural potentials.