We refine the computation of thed −ū flavor asymmetry in the proton sea with a complementary effort to reveal the dynamics of pion exchange in high-energy processes. In particular, we discuss the efficacy of pion exchange models to simultaneously describe leading neutron electroproduction at HERA along with thed −ū flavor asymmetry in the proton. A detailed χ 2 analysis of the ZEUS and H1 cross sections, when combined with constraints on the pion flux from Drell-Yan data, allows regions of applicability of one-pion exchange to be delineated. The analysis disfavors several models of the pion flux used in the literature, and yields an improved extraction of the pion structure function and its uncertainties at parton momentum fractions in the pion of 4 × 10 −4 x π 0.05 at a scale of Q 2 = 10 GeV 2 . Based on the fit results, we also address a possible estimate for leading proton structure functions in upcoming tagged deep-inelastic scattering experiments at Jefferson Lab on the deuteron with forward protons.