Over the past decade, there has been a significant development in wearable health technologies for diagnosis and monitoring, including application to stress monitoring. Most of the wearable stress monitoring systems are built on a supervised learning classification algorithm. These systems rely on the collection of sensor and reference data during the development phase. One of the most challenging tasks in physiological or pathological stress monitoring is the labeling of the physiological signals collected during an experiment. Commonly, different types of self-reporting questionnaires are used to label the perceived stress instances. These questionnaires only capture stress levels at a specific point in time. Moreover, self-reporting is subjective and prone to inaccuracies. This paper explores the potential feasibility of unsupervised learning clustering classifiers such as Affinity Propagation, Balanced Iterative Reducing and Clustering using Hierarchies (BIRCH), K-mean, Mini-Batch K-mean, Mean Shift, Density-Based Spatial Clustering of Applications with Noise (DBSCAN) and Ordering Points To Identify the Clustering Structure (OPTICS) for implementation in stress monitoring wearable devices. Traditional supervised machine learning (linear, ensembles, trees, and neighboring models) classifiers require hand-crafted features and labels while on the other hand, the unsupervised classifier does not require any labels of perceived stress levels and performs classification based on clustering algorithms. The classification results of unsupervised machine learning classifiers are found comparable to supervised machine learning classifiers on two publicly available datasets. The analysis and results of this comparative study demonstrate the potential of unsupervised learning for the development of non-invasive, continuous, and robust detection and monitoring of physiological and pathological stress.