Although overuse of the internet has been suggested to be related to poor academic performance, the effects of internet use for education on academic performance showed conflict results in previous studies. Accordingly, the associations of school performance with internet use for study and for general purpose were explored in a large population of Korean adolescents. Cross-sectional data from the 2013 Korean Youth Risk Behaviour Web-based Survey (KYRBWS) were retrieved for 59,105 12- to 18-year-old adolescents. The associations between school performance and internet use were analysed using multinomial logistic regression with complex sampling. Days of physical activity, sex, obesity, region of residence, income level, parental education level, stress, sleep time, smoking, alcohol consumption, drug use, and total study time were recorded and adjusted for as confounders. Higher school performance was positively associated with longer internet use for study (adjusted odds ratio, AOR, of 2+ h [95% confidence interval] = 2.43 [2.10–2.82], 2.02 [1.78–2.30], 1.66 [1.46–1.89], and 1.30 [1.15–1.47] for performance groups A, B, C, and D, respectively, P < 0.001) but negatively associated with longer internet use for general purpose (AOR of 3+ h [95% confidence interval] = 0.68 [0.60–0.78], 0.85 [0.76–0.94], 0.83 [0.75–0.92], and 0.98 [0.89–1.08] for performance groups A, B, C, and D, respectively, P < 0.001). Higher school performance significantly positively correlated with internet use for study but negatively correlated with internet use for general purpose. Academic use of the internet could be a means of achieving good school performance.