Sensitization to continued nociceptive stimulation is supposed to be involved in the development of chronic pain at several levels of the CNS, but experimental studies investigating the perceptual dynamics of sensitization in humans are rare, and the diagnostic validity of experimental pain models is not known. The present study used a tonic heat paradigm to assess early sensitization (15–100 s) to experimental pain in 30 chronic pain patients (15 musculoskeletal/back pain, 15 headache) and 23 healthy controls. Change in pain sensation during prolonged stimulation was measured by a dual sensitization method which combines subjective ratings and behavioural responses in an indirect psychophysical protocol protected against response bias. Phasic and tonic pain thresholds were measured for control purposes. The degree of sensitization was linearly related to stimulus temperature, and groups differed significantly in this ‘sensitization gradient’: chronic pain patients sensitized earlier and stronger than healthy subjects, musculoskeletal pain patients showed the strongest effect. Pain thresholds were lowered in headache patients only. Discriminant analysis demonstrated good sensitivity and specificity of individual sensitization measures for distinguishing pain syndromes, particularly in combination with pain thresholds. The results are in accordance with current models of spinal plasticity contributing to pathological pain states. They argue for the diagnostic value of psychophysical measures of sensitization.