Passive infrared (IR) systems enable rapid detection of chemical vapors but are limited by size, weight, cost, and power. Previously, the authors reported a novel passive sensor that utilizes multiple IR filter/detector combinations to discriminate between different chemical vapors based on their unique IR absorption spectra in the same manner the human eye uses to generate colors. This approach enables a very small, compact, and low-power sensor system with the capability to discriminate between chemical vapors of interest and background chemicals. All previous work showed the capability of this sensor system in discriminating chemical vapors against a hot blackbody in a laboratory environment. Now the authors demonstrate the ability of this sensor system to discriminate between the chemical vapor agent simulant dimethyl methylphosphonate and ethanol against the cold sky in an outdoor environment.