A student’s appraisal of tests, and associated psychological challenge and threat states, impacts their performance and experience on these tests. The present investigation of 244 high school students sought to identify salient challenge and threat orientations to science tests that may provide insights into how to optimize students’ outcomes in, and experience of, science. It did so by augmenting “traditional” educational psychology challenge and threat measures with relatively novel biopsychological measures. Latent profile analysis was conducted using five indicators: psychoeducational indicators of challenge and threat (via self-reports of self-efficacy and anxiety, respectively), neuropsychological indicators of internal attention (via electroencephalogram-alpha), and working memory activity (via electroencephalogram-theta), and a physiopsychological indicator of sympathetic arousal (via electrodermal activity). Latent profile analysis revealed four profiles representing distinct groups of high school students’ psychological orientations to test-taking: confident striders, confident battlers, ambivalents, and fearers. Each of these profiles had distinct associations with students’ test achievement and enjoyment and revealed that the inclusion of biopsychological measures augmented what would have been unearthed by self-reported educational psychology measures alone. Findings provide important insights into the extent to which the inclusion of biopsychology indicators, alongside educational psychology indicators, adds to our understanding of students’ challenge–threat orientations when they are faced with task demands such as tests.