The on-board methanol steam reforming (MSR) has long been considered as an effective approach to in-situ produce hydrogen for fuel cell vehicles (FCVs). However, the conventional MSR catalyst pellets suffer from easy breakage during the vehicle movement, leading to increased pressure drop and reduced system stability. Herein, we introduce an integrated method to prepare the highly controlled structured catalysts based on coupled processes: direct prototyping the structured substrate using digital light processing (DLP) 3D printing technology, in-situ dynamic crystallization of active components assisted by magnetic resonance imaging (MRI) and calcination. The synthesized catalyst owns a gradient layer of active component, and exhibits better MSR performance, higher mechanical strength, reduced pressure drop, higher Cu dispersion and better adhesion of active compounds when compared with the conventional powder and pellet catalysts. The demonstrated successful application proves the feasibility of developed method, which has great potential to be used for preparing precisely other monolithic catalysts with customized structures.