Quantum‐mechanically coupled well systems consisting of two GaAs wells 30 A˚ thick separated by an Al0.5Ga0.5As barrier whose thickness was varied from 12 to 40 A˚ have been grown by metalorganic chemical vapor deposition. The photoluminescence spectra of these systems indicated the splitting of a degenerate single well state into a doublet state, a symmetrical state, and an antisymmetric state. The location of the spectrum peak and shoulders agreed well with the calculated energies using Dingle’s connection rule which assumes 85% conduction band offset and the continuous first derivative of the wave function across the AlGaAs/GaAs heterojunction. Two other connection rules were tried, but the agreement was worse.