This cross-sectional study explored the relationship between 24-hour movement behaviors and executive function (EF) in preschool children. A total of 426 Han Chinese preschoolers (231 males; 3.8 ± 0.6 years old) from Zhuhai, Guangdong Province, China were selected from October 2021 to December 2021. Accelerometers were used to measure physical activity (PA) and sedentary behavior (SB), while sleep duration was obtained via a parent-report questionnaire. Components of EF (cognitive flexibility, inhibitory control, and working memory) were assessed using computerized behavioral tasks. The daily composition was significantly associated with inhibitory control and working memory. Inhibitory control improvements were linked to the addition of moderate-to-vigorous physical activity (MVPA) at the expense of SB and sleep. The reallocation between MVPA, SB, sleep, and light physical activity yielded a significant association with working memory.