The Navy program, Damage Control Automation for Reduced Manning (DC-ARM), is focused on enhancing automation of ship functions and damage control systems. A key element to this objective is the improvement of current fire detection systems. As in many applications, it is desired to increase detection sensitivity and, more importantly, increase the reliability of the detection system through improved nuisance alarm immunity. Improved reliability is needed such that fire detection systems can automatically control fire suppression systems. The use of multi-criteria-based detection technology continues to offer the most promising means to achieve both improved sensitivity to real fires and reduced susceptibility to nuisance alarm sources. A multi-signature early warning fire detection system is being developed to provide reliable warning of actual fire conditions in less time with fewer nuisance alarms than can be achieved with commercially available smoke detection systems. In this study, a large database consisting of the responses of 20 sensors to several different types of fires and nuisance sources was generated and analyzed using a variety of multivariate methods. Three data matrices were developed at discrete times corresponding to the different alarm levels of a conventional photoelectric smoke detector. The alarm times represent 0.82%, 1.63% and 11% obscurations per meter. The datasets were organized into three classes representing the sensor responses for baseline (nonfire), fires and nuisance sources. A robust data analysis strategy for use with a sensor array consisting of four to five sensors for early fire detection and nuisance source rejection was developed using a probabilistic neural network (PNN) that was developed at the Naval Research Laboratory for chemical sensor arrays. The analysis algorithms described in this paper evaluate discrete samples and develop classification models that examine individual chemical signatures at discrete points.