In this study, a theoretical investigation of intersubband nonlinear optical rectification in AlxlGa1-xlAs/GaAs/Al xrGa1-xrAs asymmetric rectangular quantum wells is presented. The electronic states in the asymmetric rectangular quantum well are described within the framework of the envelope function approach including the effects of band nonparabolicity and the effective mass mismatch. The nonlinear optical rectification is calculated using the density matrix formalism. It is found that the nonlinear optical rectification in the asymmetric rectangular quantum well depends sensitively on the parameters such as the width and the asymmetry of the potential well. The adjustable parameters allow for tuning of the asymmetric rectangular quantum well system to the desired wavelength while retaining a large optical rectification coefficient. This gives a new degree of freedom in various device applications based on nonlinear optical properties. Band nonparabolicity is found to significantly influence both electronic states and nonlinear optical rectification. Moreover the resulting optical rectification coefficient is much larger than the ones for bulk GaAs and some other theoretical studies in literature. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.