Bifunctional reagents that serve as dual coupling partners with an activating species have emerged as valuable synthetic tools in organic chemistry. They allow for the development of diverse reaction modes with enhanced efficiency and structural variability, which is in high demand for atom-economic and sustainable synthesis. Among them, bifunctional reagents containing N-heteroaryl groups have received much attention due to their ability to introduce privileged N-heteroaryl moieties into complex molecules that are otherwise challenging to access. Furthermore, these reagents have been employed under visible-light conditions to achieve various synthetic applications, enabling difunctionalization of alkenes, alkynes, and [1.1.1]propellanes under mild reaction conditions, providing access to highly functionalized N-heteroarenes. In this review, we provide an overview of the recent achievements and applications of photoinduced difunctionalization using bifunctional reagents containing N-heteroaryl groups. We systematically categorize the representative contributions in the field based on bifunctional reagents and their reactivity patterns. This review aims to highlight the potential of these reagents as powerful synthetic tools for sustainable and diverse synthesis.