The kinetics of adsorption and absorption of atomic hydrogen on a sulfur-covered V(100) surface has been studied using thermal desorption spectroscopy. The sulfur overlayer exhibited an inverse c(root 2x3 root2)R45 degrees structure, as observed by low-energy electron diffraction, corresponding to a coverage of 0.66 monolayer, The initial sticking coefficient for atomic hydrogen on this surface at 90 K is 0.16; for molecular hydrogen it is smaller than 1 x 10(-4). Most of the adsorbed hydrogen diffuses into the bulk, even at liquid N-2 temperature. The surface hydrogen desorbs in the temperature range of 150-300 K, whereas the absorbed hydrogen desorbs above 800 K. The dynamics of molecular hydrogen desorption has been studied with resonance-enhanced multiphoton ionization time-of-flight spectroscopy. It turns out that the hydrogen molecules desorbing from the vanadium surface at 950 K are vibrationally hot (60 times overpopulation of the upsilon = 1 state), but rotationally cold (T-rot = 550 K).