Internal quantum efficiency (IQE) is an important figure of merit for photoelectric applications. While the InAs core/shell (c/s) nanowire (NW) is a promising solution for efficient quantum emission, the relationship between the IQE and shell coating remains unclear. This Letter reports mid-infrared PL measurements on InAs/InGaAs, InAs/AlSb, and InAs/GaSb c/s NWs, together with bare InAs NWs as a reference. Analyses show that the IQE is depressed by a shell coating at 9 K but gets improved by up to approximately 50% for the InGaAs shell coating at 40 –140 K and up to approximately 20% beyond 110 K for the AlSb shell. The effect is ascribed not only to the crystal quality but more importantly to the radial band alignment. The result indicates the high-temperature IQE improvement of the type-I and type-II c/s NWs and the appropriateness of the mid-infrared PL analyses for narrow-gap NW evaluation.