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The development of sensors with high sensitivity, selectivity, long-term stability and other excellent performances is still the focus of current research on gas sensors. In this paper, biomorphic zinc oxide composite reduced graphene oxide nanomaterials (C–Z–ZnO–rGO) based on a metal–organic framework are synthesized by an impregnation calcination method using cotton as a biological template. The microscopic morphologies and structural composition of the composites are characterized. The response value of C–Z–ZnO–rGO to acetic acid gas is much higher than that of other gas sensors. At an operating temperature of 350 °C, the C–Z–ZnO–rGO gas-sensitive sensors have a response value of 410 for 100 ppm acetic acid, a response time of 43 s, and a recovery time of 18 s, and have good repeatability and long-term stability. The response value of 2.614 for 1 ppm of acetic acid gas further indicates that the C–Z–ZnO–rGO sensor has a low detection limit. The hollow structure of the C–Z–ZnO–rGO composites has the advantages of high specific surface area, multiple pores, diverse structures and abundant active sites, which improves the adsorption performance on acetic acid gas. [ABSTRACT FROM AUTHOR]