We show that it is possible to extract the weak mixing angle alpha via a measurement of the rate for B+/--->pi(+/-)e(+)e(-). The sensitivity to cosalpha results from the interference between the long and short distance contributions. The short distance contribution is given in terms of semileptonic form factors. The long distance contribution can be calculated using Ward identities and a short distance operator product expansion if the invariant mass of the lepton pair, q(2), is larger than Lambda(2)(QCD). For q(2)>/=2 GeV2 the branching fraction is approximately 1x10(-8)|V(td)/0.008|(2). The shape of dgamma/dq(2) is very sensitive to the value of cosalpha at small values of q(2) and varies by 50% when -1<cosalpha<1 at q(2) = 2 GeV2.