The first example of rhodium-catalyzed nondirected C-H activation/annulation reactions for the construction of fused heterocyclic cations is reported herein with excellent regioselectivity. Deuterium-labeling experiments indicated that the C(sp 3 )-H bond cleavage of the N -methyl group might be the rate-limiting step during the reaction process. This protocol provides an opportunity to rapidly access highly π-conjugated fused heterocyclic cations, which opens up a new avenue for efficient screening of single-molecular white-light-emitting materials, pure red-light-emitting materials, and π-conjugated radical materials. Importantly, novel white-light-emitting materials exhibited distinct anti-Kasha dual-emission and could rapidly be fabricated into robust organic and low-cost white light-emitting diodes.