Summary Here, dual O- and N-doped carbon nanofibrous microspheres (CNMs) promoting the chemical transformation of alkane with CO have been achieved smoothly. Efficient conversion of bulk chemicals is of great significance in chemical synthesis. Carbonylation involving CO is an important process for constructing carbonyl compounds in industry and academia, among which stands out metal-catalyzed carbonylation. However, the strong coordination ability and reducibility of CO usually lower the activity of metal catalysts. Hence, it becomes urgent to explore novel conversion strategies, such as fabricating new materials to replace traditional catalysts. In this work, we show that chitin-derived CNMs mediate oxidative double carbonylation of alkanes for the preparation of various alkyl α-ketoamides. In our findings, the porous CNM with large surface area could supply potential adhesion sites for amines, which inhibited the oxidative decomposition of amines to promote this transformation. Notably, to our knowledge, oxidative double carbonylation of the alkane C(sp3)–H bond has not yet been reported.