Cross sections for inclusive direct photon production in π−p, π+p, and pp collisions at 300 GeV/c are measured at transverse momenta pT up to 7 GeV/c (xT=0.6). For π−p→γX also the rapidity distribution is presented. The cross-section ratio σ(π−p→γX)/σ(π+p→γX) is found to be 1 at pT=4 GeV/c and rises with increasing pT. This observation signals the occurrence of valence-quark–antiquark annihilation. The results are in good agreement with QCD predictions.