Structural investigations of N-methylformamide-water mixtures (NMF-water) are performed at room temperature and atmospheric pressure for two water molar fractions x w = 0.66 and x w = 0.75 . This paper extends our recent study on the equimolar system. H-bond networks are preferentially formed between NMF and water molecules. Among a large variety of DFT optimized models, X-ray scattering data shows that the local order of each mixture is better described by a tetramer where one NMF molecule is connected to three water molecules. No self-association is observed in the considered systems. The effect of hydration is compared to the temperature and pressure effects in some hydrogen-bonded liquids.