Developing effective preference modification paradigms is crucial to improve the quality of life in a wide range of behaviors. The cue-approach training (CAT) paradigm has been introduced as an effective tool to modify preferences lasting months, without external reinforcements, using the mere association of images with a cue and a speeded button response. In the current work for the first time, we used fMRI with faces as stimuli in the CAT paradigm, focusing on face-selective brain regions. We found a behavioral change effect of CAT with faces immediately and 1-month after training, however face-selective regions were not indicative of behavioral change and thus preference change is less likely to rely on face processing brain regions.Nevertheless, we found that during training, fMRI activations in the ventral striatum were correlated with individual preference change. We also found a correlation between preference change and activations in the ventromedial prefrontal cortex during the binary choice phase. Functional connectivity among striatum, prefrontal regions, and high-level visual regions was also related to individual preference change. Our work sheds new light on the involvement of neural mechanisms in the process of valuation. This could lead to development of novel real-world interventions.