Achieving both high specificity and sensitivity are essential for gas phase chemical detection systems. Recent implementation of Metal-Organic Frameworks (MOFs) have shown great success in separation and storage systems for specific gas molecules. By implementing a MOF structure comprised of Zn(2+) coordinated trans-stilbene derivatives, a gas responsive material has been created which exhibits a high photoluminescence quantum yield, offering new opportunities for chemical sensors. Here, we reveal a nanocomposite material, assembled from azobenzene functionalized graphene oxide and stilbene-MOF, that is capable of luminescent quenching by explosive gases. This unique system displays selectivity to dinitrotoluene (71% quenching) over trinitrotoluene (20% quenching) with sub ppm sensitivity and response times of less than a minute. We show that this implementation of a graphene-based MOF composite provides a unique strategy in the development of molecularly well-defined materials having rapid, reversible, and gas selective fluorescent quenching capabilities. This opens the way for new advances in the assembly of low density frameworks using isomerization suppressed materials.