The purpose of this study was to examine the reliability and validity of the School Anxiety Inventory (SAI) using a sample of 646 Slovenian adolescents (48% boys), ranging in age from 12 to 19 years. Single confirmatory factor analyses replicated the correlated four-factor structure of scores on the SAI for anxiety-provoking school situations (Anxiety about School Failure and Punishment, Anxiety about Aggression, Anxiety about Social Evaluation, and Anxiety about Academic Evaluation), and the three-factor structure of the anxiety response systems (Physiological Anxiety, Cognitive Anxiety, and Behavioral Anxiety). Equality of factor structures was compared using multigroup confirmatory factor analyses. Measurement invariance for the four- and three-factor models was obtained across gender and school-level samples. The scores of the instrument showed high internal reliability and adequate test-retest reliability. The concurrent validity of the SAI scores was also examined through its relationship with the Social Anxiety Scale for Adolescents (SASA) scores and the Questionnaire about Interpersonal Difficulties for Adolescents (QIDA) scores. Correlations of the SAI scores with scores on the SASA and the QIDA were of low to moderate effect sizes.