Low magnetic field 2 MHz NMR relaxometry is applied to measure water adsorption processes of intact corn stover anatomical fractions. Comparison with high magnetic field 250 MHz relaxometry of milled corn stover fractions as a function of water activity, i.e., relative humidity, provides insight into the microstructural changes of the biomass and varying water molecular dynamics during adsorption. The data presented establish a basis for low field portable NMR of biomass in situ in field and processing environments.