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Overweight and obesity in childhood is associated with negative physical and psychological effects. It has been proposed that obesity increase the risk for developing cognitive deficits, dementia and Alzheimer's disease and that it may be associated with marked differences in specific brain structure volumes.The purpose of this study was a neurobiopsychological approach to examine the association between overweight and obesity, brain structure and a paediatric neuropsychological assessment in Mexican children between 6 and 8 years of age.We investigated the relation between the body mass index (BMI), brain volumetric segmentation of subcortical gray and white matter regions obtained with magnetic resonance imaging and the Neuropsychological Assessment of Children standardized for Latin America. Thirty-three healthy Mexican children between 6 and 8 years of age, divided into normal weight (18 children) and overweight/obese (15 children) groups.Overweight/obese children showed reduced executive cognitive performance on neuropsychological evaluations (i.e. verbal fluidity, P = 0.03) and presented differences in brain structures related to learning and memory (reduced left hippocampal volumes, P = 0.04) and executive functions (larger white matter volumes in the left cerebellum, P = 0.04 and mid-posterior corpus callosum, P = 0.03). Additionally, we found a positive correlation between BMI and left globulus pallidus (P = 0.012, ρ = 0.43) volume and a negative correlation between BMI and neuropsychological evaluation scores (P = 0.033, ρ = -0.37).The findings contribute to the idea that there is a relationship between BMI, executive cognitive performance and brain structure that may underlie the causal chain that leads to obesity in adulthood.