This article contains two-dimensional (2D) NMR experimental data for a series of methylcellulose (MC) with different substitution degrees (DS), obtained by the Bruker BioSpin 500 MHz NMR spectrometer (Germany). The data facilitated the 1H and 13C chemical shifts of eight anhydroglucose units (AGUs) comprising MC chains–unsubstituted, 2-mono-, 3-mono-, 6-mono-, 2,3-di-, 2,6-di-, 3,6-di-, and 2,3,6-tri-substituted AGUs. Data include analyzed the 2D NMR spectra of the MC samples, which are related to the subject of an article in Carbohydrate Polymers, entitled “NMR characterization of methylcellulose: Chemical shift assignment and mole fraction of monomers in the polymer chains” (Kon et al., 2017) [1]. These data can be very helpful to assign the 1H and 13C chemical shifts of the other cellulose derivatives, especially cellulose ethers.