Hot carrier solar cells offer the potential to exceed the Shockley–Queisser limit. So far, however, there has been no clear route to achieve this result. Recently, the exploitation of the satellite valleys of the solar absorber material has been proposed as a feasible approach to harness hot carriers. Here, we show that, upon photoinduced and field-aided intervalley scattering to upper L-valleys, hot carriers can be harnessed in InGaAs/AlInAs heterojunctions at voltages defined by the upper valley (~1.25 V in the ideal case) rather than the bandgap of the InGaAs absorber (0.75 eV) under practical operational conditions. The efficiency of the present system does not exceed the single bandgap limit due to a mismatch in the valley degeneracy across the n+-AlInAs/n-InGaAs interface. However, we suggest that this is not a fundamental limitation to the realization of a hot carrier solar cell.