We present the results of an experimental investigation on the relationship between heart rate variability (HRV) and flow in adults exposed to computer-simulated tasks with different demand level manipulations: a balanced skill-demand level (fit) to induce flow, too high demands to induce anxiety, and too low demands to induce boredom. Eighteen participants were exposed to three simulated driving tasks that differed in their demand levels. During all tasks, the participants’ heart rates were monitored and flow was measured after each task by means of a questionnaire. Our results show that high-frequency HRV (HF-HRV) and low-frequency HRV (LF-HRV) differed between the three experimental conditions and an increase in demand level caused a decrease in HF-HRV and LF-HRV. Furthermore, experiencing flow in a balanced skill-demand task was associated with a decreased LFHRV activity compared to being engaged in a task with too high demands (anxiety condition), in which higher levels of flow were related to moderate parasympathetic activity (HF-HRV) as well as to moderate baroreflex function (LF-HRV). Our results contribute to a better understanding of the psychophysiology of flow and further demonstrate how virtual environments such a driving simulator can be effectively used to investigate psychological constructs such as flow or anxiety.