m-Xylene is a volatile organic compound that is extensively used in various industrial processes. It is toxic, posing significant risks to human health and the environment. Therefore, developing gas sensors with high sensitivity and selectivity for m-xylene detection is critical. In this work, we demonstrated the synthesis of NiO-yolk double-shell (NiO-YDS) and NiO-yolk triple-shell (NiO-YTS) derived from NiO/Ni-BTC and NiO/Ni-PTA composites, respectively, using the microwave-assisted solvothermal method from Ni-BTC-derived NiO spheres. The NiO/Ni-BTC composite has trimesic acid (H3BTC) as an organic linker, while NiO/Ni-PTA has p-terephthalic acid (PTA). We investigated the sensing properties of these materials for 2-butanone, 2-nonanone, 3-methyl-1-butanol, acetone, benzene, ethanol, methanol, and m-xylene. These composites exhibited excellent sensitivity and selectivity for detecting m-xylene under dry conditions. Specifically, the NiO-YTS sensor showed a sensitivity of 217.5% to m-xylene, while the NiO-YDS sensor demonstrated a sensitivity of 179.8% at 350 °C in dry air. We emphasize the NiO-YTS composite due to its superior sensitivity and selectivity in detecting m-xylene compared with the NiO-YDS composite. The NiO-YTS sensor exhibited stable and reproducible sensing performance for 100 ppm of m-xylene under optimum working conditions, with a theoretical detection limit of 5.43 ppb and relatively fast response time (89 s) and recovery time (191 s). This work describes an easy method for synthesizing NiO-YDS and NiO-YTS derived from NiO/Ni-BTC and NiO/Ni-PTA composites. It demonstrates that these composites represent a new class of materials that can potentially enhance the sensitivity and selectivity of m-xylene gas sensors.