We propose an engineering of the optical properties of GaAs/AlGaAs quantum wells using AlAs and InAs monolayer insertions. A quantitative study of the effects of the monolayer position and the well thickness on the interband and intersubband transitions, based on the extended-basis sp 3 d 5 s * tight-binding model, is presented. The effect of insertion on the interband transitions is compared with existing experimental data. As for intersubband transitions, we show that in a GaAs/AlGaAs quantum well including two AlAs and one InAs insertions, a three level {e1, e2, e3} system where the transition energy e3 − e2 is lower and the transition energy e2 − e1 larger than the longitudinal optical phonon energy (36 meV) can be engineered together with a e3 − e2 transition energy widely tunable through the TeraHertz range.