In this work, we report on the growth of high yield small bandgap InAs and InAsSb inserts embedded in InAsP nanowires grown on an InP substrate by catalyst-free selective-area metal-organic chemical vapor deposition. It is observed that the growth of the inserts with high aspect ratios can be achieved by properly tuning the V/III ratio. Nanowire arrays with InAs(Sb) inserts exhibit strong photoluminescence at 77 K from interband transitions, spanning a wavelength range of 2.30–3.70 µm. In addition, the InAsP/InAs heterointerfaces are characterized by a scanning transmission electron microscope and an energy-dispersive X-ray spectroscopy. We believe that these results pave the way to engineering interband transitions and enabling hybrid integration for nanoscale optical devices at the mid-wavelength infrared.