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Core temperature (CT) in combination with heart rate (HR) can be a good indicator of impending heat exhaustion for occupations involving exposure to heat, heavy workloads, and wearing protective clothing. However, continuously measuring CT in an ambulatory environment is difficult. To address this problem we developed a model to estimate the time course of CT using a series of HR measurements as a leading indicator using a Kalman filter. The model was trained using data from 17 volunteers engaged in a 24 h military field exercise (air temperatures 24–36 °C, and 42%–97% relative humidity and CTs ranging from 36.0–40.0 °C). Validation data from laboratory and field studies (N = 83) encompassing various combinations of temperature, hydration, clothing, and acclimation state were examined using the Bland–Altman limits of agreement (LoA) method. We found our model had an overall bias of −0.03 ± 0.32 °C and that 95% of all CT estimates fall within ±0.63 °C (>52 000 total observations). While the model for estimating CT is not a replacement for direct measurement of CT (literature comparisons of esophageal and rectal methods average LoAs of ±0.58 °C) our results suggest it is accurate enough to provide practical indication of thermal work strain for use in the work place.