We conducted a detailed investigation of the potential structure within GaNAs/GaAs multiple quantum wells (MQWs) using three independent experimental techniques: the temperature dependence of Photo‐luminescence (PL) spectroscopy, time‐resolved PL spectroscopy, and degenerate four‐wave mixing (DFWM) measurements. We observed a very long lifetime (T1 = 12 ns) and dephasing time (T2 = 130 ps) of excitons in the GaNAs/GaAs MQWs. We suggested that the GaNAs/GaAs MQWs have a strong and deep confinement structure that is comparable to that of quantum dots (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)