The first example of photocatalytic dehydrogenative cross-coupling of electron-poor alkenes with azoles has been reported. This method provides a novel approach for N-vinylazole synthesis, which enables coupling of a broad scope of azoles and electron-deficient alkenes in an atom- and redox-economical manner. The present work opens up a new avenue to rapidly access mild C(sp²)–H amination by using rose bengal as an organophotocatalyst. The mild conditions, easy availability of alkenes and operational simplicity make the reaction useful in the synthesis of diverse substituted N-vinylazoles.