The k-nearest neighbour (kNN) rule, which naturally handles the possible non-linearity of data, is introduced to solve the fault detection problem of gas sensor arrays. In traditional fault detection methods based on the kNN rule, the detection process of each new test sample involves all samples in the entire training sample set. Therefore, these methods can be computation intensive in monitoring processes with a large volume of variables and training samples and may be impossible for real-time monitoring. To address this problem, a novel clustering-kNN rule is presented. The landmark-based spectral clustering (LSC) algorithm, which has low computational complexity, is employed to divide the entire training sample set into several clusters. Further, the kNN rule is only conducted in the cluster that is nearest to the test sample; thus, the efficiency of the fault detection methods can be enhanced by reducing the number of training samples involved in the detection process of each test sample. The performance of the proposed clustering-kNN rule is fully verified in numerical simulations with both linear and non-linear models and a real gas sensor array experimental system with different kinds of faults. The results of simulations and experiments demonstrate that the clustering-kNN rule can greatly enhance both the accuracy and efficiency of fault detection methods and provide an excellent solution to reliable and real-time monitoring of gas sensor arrays.