Mid-infrared GaAs1-xSbx/InP core/shell nanowires are grown coherently with perfectly twin-free zinc blende crystal structure. An unusual triangular InP shell with predominantly {112}A facets instead of {112}B facets is reported. It is found that this polarity preference is due to the surfactant role of Sb, which inhibits InP shell growth rate in the 112A directions. This behavior reveals a new degree of control and tunability allowed in manipulating nanowire facet geometry and polarity in radial heterostructures by a simple means. Tuning the Sb composition in the core yields controllable intense photoluminescence emission in both the 1.3 and 1.5 m optical telecommunication windows, up to room temperature for single nanowires. The internal quantum efficiency of the core/shell nanowires is experimentally determined to be as high as 56% at room temperature. Transient Rayleigh scattering analysis brings complementary information, revealing the photoexcited carrier lifetime in the core/shell nanowire to be approximate to 100 ps at 300 K and approximate to 800 ps at 10 K. In comparison, the carrier lifetime of core-only nanowire is below the detection limit of the system (25 ps). The demonstrated superior optical quality of the core/shell nanowires and their ideal emission wavelength range makes them highly relevant candidates for near-infrared optoelectronic applications.