Many security settings rely on the identity matching of unfamiliar people, which has led this task to be studied extensively in Cognitive Psychology. In these experiments, observers typically decide whether pairs of faces depict one person (an identity match) or two different people (an identity mismatch). The visual similarity of the to-be-compared faces must play a primary role in how observers accurately resolve this task, but the nature of this similarity-accuracy relationship is unclear. The current study investigated the association between accuracy and facial similarity at the level of individual items (Experiment 1 and 2) and facial features (Experiment 3 and 4). All experiments demonstrate a strong link between similarity and matching accuracy, indicating that this forms the basis of identification decisions. At a feature level, however, similarity exhibited distinct relationships with match and mismatch accuracy. In matches, similarity information was generally shared across the features of a face pair under comparison, with greater similarity linked to higher accuracy. Conversely, features within mismatching face pairs exhibited greater variation in similarity information. This indicates that identity matches and mismatches are characterised by different similarity profiles, which present distinct challenges to the cognitive system. We propose that these identification decisions can be resolved through the accumulation of convergent featural information in matches and the evaluation of divergent featural information in mismatches.