Interband transitions in GaInNAsSb/GaAs single quantum wells (SQWs) with nominally identical nitrogen and antimony concentrations (2.5% N and 7% Sb) and varying indium concentrations (from 8% to 32%) have been investigated by contactless electroreflectance (CER). CER features related to optical transitions between the ground and excited states have been clearly observed. Energies of the QW transitions extracted from CER measurements have been matched with those obtained from theoretical calculations performed within the effective mass approximation for various conduction-band offsets (QC) and various electron effective masses. It has been found that the QC increases from 40% to 80% with the rise of the indium content from 8% to 32% and the electron effective mass is close to 0.09m0. The results show that the band gap discontinuity in GaInNAsSb/GaAs SQWs can be broadly tuned with a change in the indium concentration.