The physical tasks of workers are demanding, particularly when performed long-term in unsuitable working position, with high frequency, heavy load, after injury, with developing damage of health or reduced performance due to advanced age. Work-related musculoskeletal disorders (WMSDs) result from overuse or develop over time. Work activities, which are frequent and repetitive, or activities with awkward postures, cause disorders that may be painful during work or at rest. There is a new technology in the market, occupational exoskeletons, which have the prerequisites for minimizing the negative consequences of workload on WMSDs. We provided pilot quantitative measurements of the ergonomic risk at one selected workplace in a Slovak automotive company with four different workers to prove our methodology using wearable wireless multi-sensor systems Captiv and Actigraph. At first, the test was performed in standard conditions without an exoskeleton. The unacceptable physical load was identified in considerable evaluated body areas—neck, hip, and shoulder. Next, the passive chair exoskeleton Chairless Chair 2.0 was used in trials as an ergonomic measure. Our intention was to determine whether an exoskeleton would be an effective tool for optimizing the workload in selected workplaces and whether the proposed unique quantitative measurement system would give reliable and quick results.