The effects on dehydration and cognitive performance from heat and/or physical activity are well established in the laboratory, although have not yet been studied for personnel working in occupations such as wildland firefighting regularly exposed to these types of conditions. This study aimed to investigate the effects of temperature and dehydration on seventy-three volunteer firefighters (35.7 ± 13.7 years, mean ± standard deviation) during a simulation of wildfire suppression under either control or hot (18–20; or 33–35 °C) temperature conditions. Results showed cognitive performance on the psychomotor vigilance task declined when participants were dehydrated in the heat and Stroop task performance was impaired when dehydrated late in the afternoon. Firefighters may be at risk of deteriorations in simple cognitive functions in the heat whilst dehydrated, although may also experience impairments in complex cognitive functions if dehydrated late in the day, irrespective of the environmental temperature.