National-level monitoring of quality of early childhood education (ECE) is key to achieving inclusive and equitable education. Most countries report structural quality while process characteristics are rarely observed at the national level. This study examined the associations between ECE and children's development in a middle-income country using data from a nationally representative sample of public centers serving Colombian children (N = 3163; M = 4.3 years, 50% girls; 42% Mestizo, 16% White, 15% Afro-Colombian, 4% Indigenous, 23% not reported). Descriptive findings evidenced low to moderate quality. Multilevel models showed several positive associations between structural and process quality and child outcomes. Results have implications for the existing literature and highlight the feasibility of quality monitoring in low- and middle-income countries.