Abstract: We have developed an eco-friendly method for synthesizing benzobacridine dione derivatives. Utilizing 2-(phenylamino)naphthalene-1,4-dione derivatives and ethyl cyanoacetate as starting materials, this process employs a copper(Ⅰ) catalytic system combined with the green oxidant tert-butyl hydroperoxide. Through a solvent-free radical tandem reaction, we successfully synthesized nine benzobacridine dione derivatives (3a-3i), achieving yields of 72% to 79%. This synthesis approach is not only environmentally benign but also operationally straightforward, requiring only simple filtration and washing without the need for column chromatographic separation. Additionally, it leverages readily accessible raw materials. Our method offers a novel and efficient pathway for synthesizing acridine dione derivatives with potential biological activity, aligning with the standards of green chemistry and sustainable practices.