This work examines the optical transitions of a GaAs double quantum ring (DQR) embedded in Al0.3Ga0.7As matrix by photoreflectance spectroscopy (PR). The GaAs DQR was grown by droplet epitaxy (DE). The optical properties of the DQR were investigated by excitation‐intensity and temperature‐dependent PR. The various optical transitions were observed in PR spectra, whereas the photoluminescence (PL) spectrum shows only the DQR and GaAs band emissions. The various optical transitions were identified for the GaAs near‐band‐edge transition, surface confined state (SCS), DQR confined state, wetting layer (WL), spin–orbital split (EGaAs + Δo), and AlGaAs band transition. PR spectroscopy can identify various optical transitions that are invisible in PL. The PR results show that the GaAs/AlGaAs DQR has complex electronic structures due to the various interfaces resulting from DE.