Magnetic resonance imaging (MRI), NMR relaxometry, thermal analysis and gravimetrical experiments are performed to study the water absorption by neat PA46 and copolymers of PA46 and PA4n (PA46-co-PA4n) with 4 mol% n = 8, 12 and 16. The observed reduction in water uptake, ingress rate and water molecular mobility with increasing value of n is explained by a combination of several physico-chemical molecular properties. The increased [CH2]/[amide] ratio and the reduced amount of crystallinity do not completely clarify the observed trends in water uptake and water molecular mobility in the copolymer series. It is shown that the increased chain mobility of the PA46 segments in the copolymers allows an improved coupling of the amide groups in the amorphous phase, explaining the observed decrease in water uptake. The important role of the morphology of the amorphous phase for water uptake is further demonstrated by annealing results and NMR relaxation experiments as a function of temperature. (C) 2004 Elsevier Ltd. All rights reserved.