A comparison between the electronic structure of the alloy Al0.5Ga0.5As and that of the superlattice [(AlAs)2/(GaAs)2]10as determined by angle‐resolved photoelectron spectroscopy is presented. Experimental data have been acquired and interpreted according to identical methodologies for the two materials. A mini band gap observed in the superlattice due to the artificially induced periodicity in the growth direction is not present in the alloy. This suggests that the alloy as grown, exhibits no evidence of self‐induced long range order. The critical point energyX3vof the alloy is found to lie closer to the value for AlAs than that for GaAs, in agreement with a nonlinear interpolation scheme, and to be higher than the Γ̄4v(X3v) point of the superlattice.