Our current work examined the interface between thinking style and emotional experience at both the behavioral and neuropsychological levels. Thirty-nine Chinese participants completed the triad task, and we calculated the rate of individually selected relationship pairings to overall selections to represent their holistic thinking tendencies. In addition, participants in the top one-third of the ratio score were classified into the high holistic thinking group, while those in the bottom one-third of the ratio score were classified into the low holistic thinking group. We used the sensitivity to punishment and sensitivity to reward questionnaire (SPSRQ) to examine how people elicit positive and negative affective behaviors. Additionally, we examined the volume of the amygdala and nucleus accumbens and their functional connectivity in the resting-state. We found that high holistic thinkers were much less sensitive to rewards than low holistic thinkers. In other words, individuals with high holistic thinking are less likely to pursue behaviors that have positive emotional outcomes. Furthermore, their bilateral nucleus accumbens and right amygdala volumes were smaller than those of low holistic thinkers. Hierarchical regression analysis showed that holistic thinking tendency can negatively predict the volume of the left nucleus accumbens and right amygdala. Finally, resting-state functional connectivity results showed increased functional connectivity FC between left nucleus accumbens and bilateral amygdala in high holistic thinkers. These findings provide emotion-related manifestations of thinking styles at the behavioral and neural levels.