This literature review investigated relations between structural characteristics and process quality in centre and family daycare provisions for children from birth to age 5. Structural characteristics were examined at system, organisational, classroom, and staff levels. The strongest evidence concerned the positive relations between staff’ pre-service and professional development and process quality. Smaller group sizes and child-staff ratios were also generally positively related to process quality. At the system level, quality rating and improvement systems appeared to be associated with higher process quality, although most systems lacked sensitivity in differentiating between fine-grained levels of quality. Evidence on relations at the organisational level was scarce. Furthermore, there was evidence of a complex interaction of structural features at different levels that jointly predicted process quality, but more research is warranted. Overall, most studies were focused on centre-based provisions for children aged 3 to 5, whereas less evidence was available for provisions for children aged 0 to 2 and family daycare.