We investigate the defect-dependent electronic structure and gas-sensing potential of cubic α-CsPbI₃ using first-principles density functional theory and nonadiabatic molecular dynamics. Among the intrinsic defects, interstitials, vacancies, antisites, and switches studied, the I_Pb and Pb_I antisite defects exhibit transition energy levels near the middle of the band gap, thus functioning as deep traps. Short-term adsorption of ammonia selectively modifies the electronic structure, coordinating with Pb at Pb_I sites and Cs at I_Pb sites, significantly altering recombination pathways. Detailed analysis reveals that NH₃ reduces anharmonicity at I_Pb defects, enabling enhanced recombination at elevated temperatures, while trap-assisted recombination dominates at room temperature. Other analytes, including CH₃NH₂ and NO₂, show negligible impact on the band gap or recombination dynamics, highlighting the potential selectivity of NH₃ interactions. Ab initio nonadiabatic molecular dynamics simulations at 300 K and 600 K further demonstrate temperature-dependent modulation of carrier lifetimes, with NH₃ accelerating recombination at ambient conditions and suppressing certain pathways at higher temperatures. These findings suggest that α-CsPbI₃ can serve as a selective and sensitive ammonia sensor over a broad temperature range and offer insights for ammonia detection under industrially relevant conditions.