In0.227GaAs/GaAsN0.011 was introduced as a 1.2-eV multiple quantum well (MQW) with a flat conduction band (FCB) in which a conduction band edge of GaAsN was adjusted to be equal to that of InGaAs. This MQW was established as a candidate material for a middle absorption layer of three-junction solar cell since electron confinement was eliminated and a short electron lifetime in GaNAs was compensated by InGaAs layer. The band alignment of MQW was characterized by the power-dependent photoluminescence (PL) measurement under low temperature. According to the band-anti crossing model, the FCB is possibly constructed since a small amount of incorporated N can drastically reduce the energy of the conduction band edge of GaAsN. The PL results demonstrated that In0.227GaAs/GaAsN MQW was a type-I structure when N content was below 1.1%, and became a type-II structure when N content was above 1.1%. The type-II MQW was characterized by the observation of blueshift of PL peak when increasing excitation power. This blueshift is a result of band-bending effect due to the accumulation of excited carriers at the interface between two materials, which is unique for the type-II MQW. In addition, it was observed that the activation energy estimated from the Arrhenius plot provided a minimum value in the structure with 1.1%N; the lowest activation energy indicated the weakest confinement energy of carriers in the structure. These results approved that a transition from type-I to type-II occurred when N content surpassed 1.1%, and our designed In0.227GaAs/GaAsN0.011 MQW was potentially the FCB structure.