In the cities in the future, seeing electric vehicles on the roads will be as ordinary an occurrence as seeing internal combustion engine cars today. Electric vehicles can greatly benefit from utilizing polymer electrolyte membrane fuel cells (PEMFCs) because they provide higher efficiency (40–50%) and are more environmentally friendly. However, there are some major drawbacks to using PEMFCs as electrical sources in vehicles; these are energy balance and management issues that must be addressed to meet vehicle power and energy requirements. Therefore, it seems that hybridizing PEMFCs with energy storage devices, such as supercapacitors (SCs), would be an efficient solution to address these drawbacks in order to accommodate driving behaviors such as dynamic loads. The goal of this research is, therefore, to demonstrate the use of a PEMFC–SC direct hybridization configuration with a dynamic stress test by simulating driving behavior in urban areas such as Bangkok. This research presents substantial advantages in energy management and voltage and material degradation. In order to achieve this objective, a quasi-static stress profile, including stationary conditions, load variations, and start–stop conditions, was specifically created for PEMFC–SC direct hybridization systems with 840 hours of operating duration. The performance, durability, and reliability of this system were investigated via polarization curves, hysteresis loops, and voltage degradation rates. Then, experimental results were compared to the degradation of the cell components. Any degradation in material components was observed through electrochemical impedance spectroscopy (EIS) and morphology studies. The characterization of materials in the PEMFC–SC direct hybridization systems via chemical and electrochemical analyses is an important approach in material invention and modification for the new generation of PEMFCs. This work strives to pave the way for PEMFC hybridization development to achieve effective commercialization.