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[Display omitted] • Calcined Ge-UTL encountered structural degradation under pure water solution at RT. • A simply ultrasonic treatment caused random arrangement of the formed cfi layers. • The stacking faults of cfi layers generated abundant intracrystal mesopores. • An excellent styrene epoxidation activity (TOF = 403 h−1) is achieved on Co-Meso-UTL. Co-zeolites with hierarchical porous are significantly desirable for the liquid-phase selective epoxidation of styrene that required relatively open reaction spaces. A typical UTL germanosilicate with the absence of organic structure-directing agent molecules inside pore channels suffered from severe structural collapse after ultrasonic treatment under pure water medium, originating from the unstable germanium-rich double four ring subunits. The simple strategy cleaved the weak linkage Ge-O bands and caused the irregular location of silicon-rich cfi layers. Subsequently, Co activity centers was incorporated into the framework through reacting with the abundant silanol groups located in the hydroxyl nests at room temperature. The random arrangement of mono- or multi- cfi layers induced the stacking faults and generated a large amount of intracrystal mesopores after calcination. The resultant Co-Meso-UTL catalysts favored the molecules diffusion of large-sized styrene and target products, improving the accessibility of Co active sites and exhibiting excellent catalytic performance in the styrene epoxidation reaction with single hydrogen peroxide (H 2 O 2) oxidant. Especially, high styrene oxide product selectivity was also obtained through controlling appropriate H 2 O 2 -added content as well as reaction time, which possessed a highest turnover frequency value of 403 h−1 among the reported catalysts. [ABSTRACT FROM AUTHOR]