The hydrogen cyanide (HCN) concentration in exhaled human breath and skin gas samples collected with different sampling techniques was measured using near-infrared cavity ring-down spectroscopy. The median baseline HCN concentrations in samples provided by 19 healthy volunteers 2-4 h after the last meal depended on the employed sampling technique: 6.5 parts per billion by volume (ppbv) in mixed (dead space and end-tidal) mouth-exhaled breath collected to a gas sampling bag, 3.9 ppbv in end-tidal mouth-exhaled breath, 1.3 ppbv in end-tidal nose-exhaled breath, 1.0 ppbv in unwashed skin and 0.6 ppbv in washed skin samples. Diurnal measurements showed that elevated HCN levels are to be expected in mouth-exhaled breath samples after food and drink intake, which suggests HCN generation in the oral cavity. The HCN concentrations in end-tidal nose-exhaled breath and skin gas samples were correlated, and it is concluded that these concentrations best reflect systemic HCN levels.