We present the first experimental discrimination between the 2e/3 and 4e/3 top quark electric charge scenarios, using top quark pairs (tt¯) produced in pp¯ collisions at s=1.96 TeV by the Fermilab Tevatron Collider. We use 370 pb−1 of data collected by the D0 experiment and select events with at least one high transverse momentum electron or muon, high transverse energy imbalance, and four or more jets. We discriminate between b- and b¯-quark jets by using the charge and momenta of tracks within the jet cones. The data are consistent with the expected electric charge, |q|=2e/3. We exclude, at the 92% C.L., that the sample is solely due to the production of exotic quark pairs QQ¯ with |q|=4e/3. We place an upper limit on the fraction of QQ¯ pairs ρ<0.80 at the 90% C.L.Received 18 August 2006DOI:https://doi.org/10.1103/PhysRevLett.98.041801©2007 American Physical Society