Poly(monomethyl itaconate) is outstanding because it is a glassy and dielectric polymer obtained from sustainable feedstock. Consequently, the study of the properties of its nanocomposites has gained importance. Herein, the electrical properties of nanocomposites based on poly(monomethyl itaconate) and functionalized few-layer graphene oxide (FGO) in the presence and absence of lithium ions (Li+) are studied. Not only did the electrical conductivities of the nanocomposites present values as high as 10(-5) Scm(-1), but also the dielectric permittivity of nanocomposites with (FGO) content lower than the percolation threshold was twice that of the pristine polymer, without presenting a drastic increase of the loss tangent. By contrast, nanocomposites containing Li+ ions presented significant increases of the permittivity with concomitant increases of the loss tangent. Moreover, it was determined that the presence of Li+ ions influenced the charge transport in the composites because of its ionic nature.