Resonant tunnelling diodes with different structures were grown. Their photoluminescence spectra were investigated. By contrast, the luminescence in the quantum well is separated from that of other epilayers. The result is obtained that the exciton of the luminescence in the quantum well is partly come from the cap layer in the experiment.So the photoluminescence spectrum is closely related to the electron transport in the resonant tunnelling diode structure.This offers a method by which the important performance of resonant tunnelling diode could be forecast by analysing the integrated photoluminescence intensities.