Cognitive decision-making is known to be deficient, but relatively less is known about emotional decision-making in schizophrenia. The Iowa gambling task (IGT) is considered a reliable probe of emotional decision-making and believed to reflect orbitofrontal cortex (OFC) function. The expectancy-valence model of IGT performance implicates three dissociable components, namely, attention to reward, memory for past, relative to recent, outcomes and impulsivity in emotional decision-making. We examined IGT performance, its three components, and their grey matter volume (GMV) correlates in 75 stable patients with schizophrenia, relative to 25 healthy individuals. Patients, relative to controls, showed impaired IGT performance and poor memory for past, relative to recent, outcomes. IGT performance correlated with GMV in the OFC in controls, but not patients. There were associations between (a) attention to reward and GMV in the frontal, temporal, parietal and striatal regions in controls, and in the temporal and thalamic regions in patients, (b) memory for past outcomes and GMV in the temporal region in controls, and the frontal and temporal regions in patients, and (c) low impulsivity and greater GMV in the frontal, temporal, posterior cingulate and occipital regions in controls, and in the frontal, temporal and posterior cingulate regions in patients. Most IGT-GMV associations were stronger in controls. It is concluded that (i) poor memory, rather than less attention to reward or impulsivity, contributes to IGT performance deficit, and (ii) the relationship of IGT performance and its components with GMVs especially in the frontal and temporal lobes is lost or attenuated in schizophrenia.