Study objective: This study aimed to examine the direct effects of environmental characteristics of early childhood education and care (ECEC) centres on adiposity, and the indirect effects through daily movement behaviours (physical activity, sedentary time and naps). Methods: 274 children (average age 19.73 ± 4.15 months) from 27 ECEC centres participated in this study. Environmental characteristics of ECEC centres were rated using the Infant/Toddler Environment Rating Scale-revised edition (ITERS-R). Daily movement behaviours were assessed using 24-h accelerometry. Body mass index z-scores were used to indicate adiposity. Results: There were no significant direct effects or indirect effects of environmental characteristics on toddlers’ adiposity through daily movement behaviours. However, the environmental characteristics of “personal care routine” (B=0.72, p = 0.041) and “activity” (B = 0.87, p < 0.050) were positively associated with the percentage of time these toddlers spent in moderate-to-vigorous physical activity (MVPA). “Listening and talking” was also positively associated withnap(s) durations (B = 4.08 p = 0.001). Conclusion: The relationships between environmental characteristics of ECEC centres and adiposity in toddlers, as well as, the mediating roles of daily movement behaviours still need confirmation by future longitudinal and experimental studies with long follow-up periods. At the same time, a broader spectrum of environmental characteristics of these settings needs to be examined with toddlers’ adiposity in future studies; other potential mediators may also need to be taken into considerations.