Aversive conditioning has been proposed as an important factor involved in the etiology of posttraumatic stress disorder (PTSD). However, it is not yet fully understood exactly which learning mechanisms are characteristic for PTSD. PTSD patients (n=36), and healthy individuals with and without trauma exposure (TE group, n=21; nTE group, n=34), underwent a differential fear conditioning experiment consisting of habituation, acquisition, and extinction phases. An electrical stimulus served as the unconditioned stimulus (US), and two neutral pictures as conditioned stimuli (CS+, paired; CS-, unpaired). Conditioned responses were quantified by skin conductance responses (SCRs), subjective ratings of CS valence and US-expectancy, and a behavioural test. In contrast to the nTE group, PTSD patients showed delayed extinction of SCRs to the CS+. Online ratings of valence and US-expectancy as well as the behavioural test confirmed this pattern. These findings point to a deficit in extinction learning and highlight the role of affective valence appraisals and cognitive biases in PTSD. In addition, there was some evidence that a subgroup of PTSD patients had difficulties in learning the CS-US contingency, thereby providing preliminary evidence of reduced discrimination learning.