Two-dimensional (2D) heterostructures endowed with mesoporosities offer exciting opportunities in electrocatalysis, photocatalysis, energy storage and conversion technologies due to their integrated functionalities, abundant active sites and shortened diffusion distance. However, layered mesostructures have not been combined due to the immense difficulties by conventional chemical, mechanical exfoliation or self-assembly approaches. Herein, we explored a bottom-up strategy, carried out under mild conditions, for the facile synthesis of monolayered mesoporous titania-mesoporous carbon vertical heterostructure with uniform mesopore size, which enables ultra-high rate capability and cycling longevity for pseudocapacitive sodium-ion storage in non-aqueous electrolyte. Such brand-new type of heterostructure consists of well-ordered monolayered mesoporous titania nanosheets and surrounding two mesoporous carbon monolayers assembled at both sides. Remarkably, the combination of interconnected large mesoporosity and heterointerface leads to highly promoted reversible pseudocapacitance (96.4% of total charge storage at a sweep rate of 1 mV s-1), and enables to retain strong mechanical stability during the rapid sodiation and desodiation processes. This study reveals the importance of incorporating mesopores into heterointerface as a strategy for enhancing charge storage kinetics of electroactive materials.