Although research suggests that particles influence cardiac autonomic response as evidenced by decreases in heart rate variability (HRV), the time course of the response remains unclear. Using a crossover panel study, we monitored 36 male boilermaker welders, occupationally exposed to metal-rich particulate matter (PM) to investigate the temporal trend of hourly HRV subsequent to PM exposure. Ambulatory electrocardiograms were collected over work (exposure) and non-work (control) periods and the mean of the standard deviations of all normal-to-normal intervals for all 5-min segments (SDNN_i) was calculated hourly for up to 14-hrs post-work. The exposure-response relationship was examined with linear mixed effects regression models to account for participants monitored over multiple occasions. Models were adjusted for non-work HRV to control for diurnal fluctuations and individual predictors of HRV. The mean (SD) work PM_{2. 5} concentration was 1.12 (0.76) mg/m³. Hourly SDNN_i was consistently lower post-work as compared to the same time period on a non-work day. HRV was inversely associated with work PM_{2. 5} exposures in each of the 14-hrs post-work. The hourly associations suggested an early and later phase response, with the largest regression coefficients observed 2-3 hrs (β = -6.86 (95% CI: -11.91, -1.81) msec/1 mg/m³ at 3-hrs), and then 9-13 hrs (β = -8.60 (95% CI: -17.45, 0.24) msec/1 mg/m³ at 11-hrs), after adjusting for non-work HRV, smoking status, and age. This investigation demonstrates declines in HRV for up to 14 hours following PM exposure and a multiphase cardiovascular autonomic response with immediate (2 hrs) and delayed (9-13 hrs) responses.