Aim: To investigate the association between white matter organization in the neonatal brain and cognitive capacities at early school age in children born very preterm. Method: Thirty children born very preterm (gestational age median 27.5wks, interquartile range [IQR] 25.5–29.5; 18 males, 12 females) were included in this retrospective observational cohort study. Diffusion-weighted imaging (DWI) had been performed on a 3T system in the neonatal period (median 41.3 [IQR 40.0–42.6]wks) and cognitive functioning was formally assessed at age 5 years and 7 months (IQR 5.4–5.9y) using the Wechsler Preschool and Primary Scale of Intelligence. Structural connectivity maps were reconstructed from the DWI data using deterministic streamline tractography. Network metrics of global and local communication and mean fractional anisotropy of white matter pathways were related to IQ and processing speed at age 5 years using linear regression analyses. Results: Mean fractional anisotropy was significantly related to Performance IQ at age 5 years (F=8.48, p=0.007). Findings persisted after adjustment for maternal education level. Interpretation: Our findings provide evidence that the blueprint of later cognitive achievement is already present at term-equivalent age and suggest that white matter connectivity strength may be a valuable predictor for long-term cognitive functioning.