In enclosed suits, such as those worn by explosive ordnance disposal (EOD) experts, evaporative cooling through perspiration is less effective and, particularly in hot environments, uncompensable heat stress (UHS) may occur. Although some suits have cooling systems, their effectiveness during missions is dependent on the operative's posture. In order to properly assess thermal state, temperature-based assessment systems need to take posture into account. This paper builds on previous work for instrumenting EOD suits with regard to temperature monitoring and proposes to also monitor operative posture with MEMS accelerometers. Posture is a key factor in predicting how body temperature will change and is therefore important in providing local or remote warning of the onset of UHS. In this work, the C4.5 decision tree algorithm is used to produce an on-line classifier that can differentiate between nine key postures from current acceleration readings. Additional features that summarize how acceleration is changing over time are used to improve average classification accuracy to around 97.2%. Without such temporal feature extraction, dynamic postures are difficult to classify accurately. Experimental results show that training over a variety of subjects, and in particular, mixing gender, improves results on unseen subjects. The main advantages of the on-line posture classification system described here are that it is accurate, does not require integration of acceleration over time, and is computationally lightweight, allowing it to be easily supported on wearable microprocessors.