The DNA-caffeine interaction at high concentration of caffeine (Cf) leads to an arrangement of Cf molecules outside of the DNA double helix with an orientation parallel to the bases both in the A and B form as demonstrated by infrared linear dichroism. Addition of DNA broadens the 1H NMR lines of Cf in aqueous solution indicating a specific binding. Intercalation is not the predominant mechanism, the deuterium relaxation time T1 = (38 +/- 7) ms and the estimated reorientation correlation time tau cb = 0.17 ns of caffeine-8[2H] in the Cf-DNA complex suggest an outside stacking of the ligand. According to the results a model on the DNA-Cf complex at high Cf concentration (binding process II) is suggested including the caffeine-induced reorientation of the hydration shell of DNA.