The idling of automobiles at street intersections can lead to pollutant accumulation which impacts the health of residents in street-facing buildings. Previous research focused on pollutant dispersion within street canyons and did not consider the coupling of indoor and outdoor pollutants. This paper employs the computational fluid dynamics (CFD) method to simulate the dispersion characteristics of vehicle emission pollutants in street canyons, primarily investigating the indoor and outdoor pollutant dispersion patterns under various window opening configurations (single-sided ventilation, corner ventilation, and different positions of the glass under corner ventilation). Additionally, the study considers the impacts of the aspect ratio and ambient wind speed. Studies have shown that corner ventilation is effective in reducing indoor pollutant levels. When the two window glass positions are far away from the center of the intersection, the average CO mass fraction in the single-sided ventilation room is reduced by 87.1%. The average indoor CO mass fraction on the leeward side decreases with the increasing wind speed and aspect ratio. At a wind speed of 8 m/s, the average indoor CO mass fraction on the leeward side decreases to 2.45 × 10−8. At an aspect ratio of 2, the indoor CO mass fraction on the leeward side decreases with increasing floors before stabilizing at approximately 4.77 × 10−9. This study suggests optimal window opening strategies to reduce indoor pollutant levels in street-facing buildings at street intersections, offering guidance to indoor residents on window ventilation practices.