With the rise of live-streaming services on e-commerce platforms, AI-powered virtual idols have demonstrated tremendous application potential and thus possess high commercial value. From the perspective of psychological distance, this study adopts the Stimulus–Organism–Response (S–O–R) theoretical framework to construct a research model of “AI-powered virtual idols–psychological distance–impulsive buying intention”. The model aims to explore how AI-powered virtual idols promote digital natives’ impulsive buying intention in the context of e-commerce live streaming. Furthermore, this study examines the moderating effect of technology readiness on the relationship between AI-powered virtual idols and psychological distance. The findings reveal that the level of intelligence of AI-powered virtual idols—including interactivity, anthropomorphism, homogeneity, and reputation—enhances digital natives’ impulsive buying intention by reducing psychological distance. For digital natives with lower technology readiness, the effect of AI-powered virtual idols in narrowing psychological distance is more pronounced. These findings enrich AI-driven consumer behavior models from a theoretical perspective and offer theoretical support and practical insights for developing AI-empowered digital marketing strategies tailored to the psychological traits and technological adaptability of digital natives.