The facile and affordable fabrication of sensors that can detect carcinogenic benzene has remained a long-standing challenge, as sophisticated nano-architectures and/or sensing films are essential to ensure benzene selectivity. Herein, we report a raisin bread-structured film fabricated by mixing two different types of oxide hollow spheres, as a novel, cost-effective platform for the highly selective and sensitive detection of benzene. The film comprises catalytic Pd-Co3O4 (i.e., raisins) and gas-sensing SnO2 hollow spheres (i.e., bread), prepared by ultrasonic spray pyrolysis. In contrast to films of pure SnO2 or Pd-Co3O4 hollow spheres, which are partially selective to reactive gases such as xylene/toluene/ethanol, raisin bread films are highly selective to less reactive benzene. Thus, an array of the SnO2, Pd-Co3O4, and raisin bread sensors enables exclusive benzene identification with principal component analysis. The superior benzene-sensing properties of raisin bread sensors are attributed to the oxidative consumption of reactive gases by the catalytic raisins, whereas less-consumed benzene sensitively reacts with the gas-sensing bread. This is supported by proton transfer reaction-quadrupole mass spectrometry analysis. This work provides a simple, rational strategy to attain gas selectivity to chemically stable benzene and is expected to trigger the development of ubiquitous portable devices to monitor airborne benzene. Display omitted •Raisin bread film is fabricated by mixing two different oxide hollow spheres.•The film shows high selectivity to benzene gas.•The sensing mechanism is confirmed via mass spectrometry-based analysis.•An electric nose composed of sensors with different gas selectivity is designed.•The exclusive identification of benzene in the electric nose is demonstrated.