This case report examines the correlation between hydration, weight variation, and perceived effort in a 43-year-old amateur athlete during a self-supported 81.5 km crossing of Death Valley, completed over 3 days with significant elevation changes. Studies have shown that a body mass loss greater than 2–3% can lead to an increased perception of effort and a decline in performance. Specifically, during passive and active heat exposures, the average body mass loss was found to be 1.4 ± 0.3% and 4.1 ± 0.7%, respectively. Salivary osmolarity has demonstrated a sensitivity of 86% and specificity of 91% in diagnosing dehydration of ≥ 2%, suggesting its potential as a non-invasive indicator of hydration status. The subject monitored their own body weight, hydration (via salivary osmolarity), and perceived effort using a rate of perceived exertion (RPE) scale. Nutritional intake included isocaloric meals and nutritional bars, and hydration was managed using water and a hydroelectrolytic solution. Key bioimpedance parameters were measured to assess body composition and hydration status. A progressive decrease in body weight correlated with an increase in perceived effort (RPE score) and salivary osmolarity. Resistance (Rx) remained stable, while reactance (Xc) showed a biphasic trend and was inversely correlated with the sodium/potassium ratio (NAK). There were significant linear correlations between perceived effort and both weight loss and salivary osmolarity, indicating that salivary osmolarity is a potential early predictor of these changes. The findings highlight a linear correlation between weight loss, perceived effort, and salivary osmolarity, suggesting that monitoring salivary osmolarity would be useful for the field assessment of hydration and exertion. Further research with larger populations is necessary to validate these observations.