Using nationally representative data from the Longitudinal Study of Australian Children (LSAC; N = 5,107), this study assessed prospective connections between children’s early education and care (EEC) experiences from infancy through preschool and their cognitive and behavioral functioning in 1st grade. Incorporating 6 waves of data, analyses found that greater duration and intensity of exposure to center EEC settings predicted heightened fluid intelligence but also decreased behavioral functioning across multiple realms and reporters. Assessment of the timing of exposure found that the combination of infant/toddler and preschool center EEC, rather than only preschool EEC, drove these patterns. Results largely replicate patterns from U.S. studies, suggesting the importance of identifying EEC programs and models that can support children’s behavioral as well as cognitive skills. In contrast to U.S. results, associations between center EEC and children’s later functioning did not extend to basic academic skills and were not moderated by family socioeconomic resources or child temperament.