We present a measurement of the electron charge asymmetry in ppbar->W+X->enu+X events at a center of mass energy of 1.96 TeV using 0.75 fb-1 of data collected with the D0 detector at the Fermilab Tevatron Collider. The asymmetry is measured as a function of the electron transverse momentum and pseudorapidity in the interval (-3.2, 3.2) and is compared with expectations from next-to-leading order calculations in perturbative quantum chromodynamics. These measurements will allow more accurate determinations of the proton parton distribution functions.