This paper reports the results of work aimed at improving the performance of LEDs and photodiodes based on InAsSb solid solutions operating in the spectral range around 4.2 μm, as well as improving the efficiency of optocouple based on them in the absorption band of carbon dioxide in a wide temperature range, including high temperatures. An increase in the characteristics of optoelectronic components was achieved: detectivity D* = 3∙1010 (cm∙√Hz)/W and LEDs’ power ~ 100 µ W (200 mA) at room temperature. Based on the obtained optoelectronic components, a non-dispersive infrared carbon dioxide sensor with a limit of detection of 0.0025 vol.%, relative error of 0.1% of measurement in the 0–10 vol.% concentration was developed. The sensor featured a 2 cm optical path, a sampling interval of 128 ms, and a power consumption of less than 50 mW.