In this study, multistacked InAs submonolayer (SML) quantum dots (QDs) were sandwiched in an InGaAs/GaAsSb dot-in-a-double-well (DDwell) structure to enhance the crystal quality and optical properties of QDs. The photoluminescence (PL) intensity of the InAs SML QDs with the DDwell structure was 5.5 times higher than that of conventional InAs/GaAs SML QDs because of the reduced number of nonradiative recombination centers and the enhanced carrier hole confinement. The PL results of the DDwell structure exhibit two peaks that represent the carrier overflow from SML QDs to InGaAs quantum wells (QWs) and hence the radiative recombination in InGaAs QWs because of the shallow carrier confinement of SML QDs. Among the compared samples, the DDwell structure exhibited the highest activation energy of 101.8 meV. Furthermore, the carrier thermal escape was suppressed in these InAs SML QDs. High-resolution transmission electron microscopy revealed that the microstructures of the InAs SML QDs demonstrated larger dots for the DDwell structure, thus verifying that the emission wavelength elongated in the PL measurement. These improved optical properties of the InAs SML QDs with the DDwell structure were attributable to the improved crystal quality because of the use of Sb surfactants and additional volume for carrier recombination provided by the InGaAs quantum well. The DDwell structure can thus be applied in optoelectronic devices to obtain advanced performance.