Metal nanoparticles and thin film assemblies are attractive as nanostructured sensing materials for chemiresistor sensors. This work focuses on the development of chemiresistor sensor arrays (CSA) with nanoparticle-structured thin films as sensing materials for the detection of volatile organic compounds (VOCs). The nanoparticle-structured thin films were derived from molecularly-mediated thin film assemblies of gold nanoparticles which can be tuned in terms of size, composition and interparticle structures. The chemiresistor sensor array detection was coupled with gas chromatographic flame ionization detector (FID) for assessing the sensitivity, selectivity and limit of detection. The results of the CSA and FID data from the detection of VOCs are analyzed and compared. The results provide useful information to aid the evaluation of our CSAs and nanostructured sensing materials. Implications of the results to the optimization of the sensor arrays will also be discussed.