This study analyzes neural responses connected to trust and risk to explain financial digitalization decisions. It shows that brain responses distinctively inform differences in the adoption of digital financial channels that are not shown by any other sociodemographic or behavioral indicators. From a methodological standpoint, the study explores if usage patterns of digital financial channels and instruments are associated with psychological and biological indicators; it uses functional magnetic resonance imaging (fMRI) to investigate whether financial digitalization decisions are linked to the evoked brain response to the safety associated with video images of financial transactions through digitalized and non-digitalized channels; it conducts trust and risk neuro-experiments to identify their impact on financial digitalization decisions and it analyzes whether brain structure is linked to financial digitalization behavior. The findings suggest that high and low frequency users exhibit differences in brain function and also in volume and fractional anisotropy values. A higher frequency of use of financial digital financial services is associated with higher brain activation linked to insecurity (lower safety neural evoked responses during the video task and an altered white matter microstructure of the cingulum). Additionally, high frequency users of digital financial channels exhibit enhanced activation of brain areas linked to emotional processing during the trust game. These findings have important implications for the design of public policies to enhance financial inclusion through technology and the segmentation and service distribution strategies of private financial institutions.