ODCR has been employed to study effective masses and carrier recombination in GaNAs/GaAs multi-quantum well (MQW) structures, prepared by MBE with the nitrogen composition up to 4.5 above GaAs bandgap excitation consists of the excitonic recombination within the GaNAs MQW, the band edge PL emissions from GaAs and a broad 0.8-eV PL of unknown origin. When monitoring these emissions under the above GaAs excitation, the ODCR spectrum is dominated by the electron and hole CR in GaAs, with effective mass values 0.07m₀ and 0.5m_0, respectively. The ODCR mechanism is discussed in terms of hot carrier effects, resulting in a reduced carrier recombination in GaAs and an enhanced carrier trapping in the GaNAs MQW. Under resonant excitation of the GaNAs MQW only a broad ODCR signal can be observed corresponding to an effective mass value 0.1m_0, attributed to the electron CR in the GaNAs MQW, where a higher electron effective mass value and a much lower mobility are expected.