Oral health status ideally warrants for a holistic biopsychosocial approach to health and wellness. Little is known about the impact of behavioral problems on oral health-related quality of life (OHRQoL) in children due to the paucity of studies in early childhood, particularly in Asian multi-ethnic populations. This study evaluated the relationship between early child's socioemotional factors and OHRQoL, as well as its association with orofacial pain (OFP) and early childhood caries (ECC) in the Asian GUSTO birth cohort. Mother-child dyads were postnatally assessed at 3 time points. The Child Behavior Checklist (CBCL) was used to assess the child's socioemotional and behavioral problems at age 4-4.5 years together with other validated questionnaires to evaluate maternal anxiety and depression. ECC detection was performed at age 5, and OHRQoL (primary) and OFP (secondary) outcomes were assessed at age 6 from a total of 555 mother-child dyads. After a univariate regression analysis was performed to identify potential predictors and confounders, a multivariate regression model was run with predisposing factors (CBCL internalization and externalization problems, OFP, ECC) and adjusted for confounders (maternal psychosocial states, maternal education) to determine associations with OHRQoL. Results showed an association between CBCL internalization scores and poorer OHRQoL (RR = 1.03, p = 0.033, 95% CI 1.01 to 1.05), although the limited risk ratio may not have a practical applicability in psychosocially healthy children, alike the majority of those evaluated in this cohort. The average OHRQoL overall score among children with OFP was 2.39 times more than those without OFP (OR = 2.39, p < 0.001, 95% CI 2.00 to 2.86). Thus, in early childhood, OFP, and to lesser extent internalizing behaviors, may negatively impact OHRQoL. This study therefore highlights the complex relationship between OHRQoL and its predisposing socioemotional and somatic pain factors, and demands further investigations in clinically relevant populations.