After a long evolution, plants not only form biomass recalcitrance but also form dense and porous anatomical structures. Originally, the function of these structures were to provide mechanical support or flow channels for nutrient transport and etc. for plants. In the field of biomass refinery, these structures can be considered as porous media where fluid flow and reactions take place. This porous media would directly influent any fluent involved process like pretreatment and hydrolysis of biomass. However, for untreated plants, the efficiency of mass transfer of pretreatment or hydrolysis is too low, which is not conductive to biorefinery processes. To be specific, the porous media of natural biomass result in low rate of liquid seepage in the biomass, which in turn hinders the mass transfer behavior of the process and can be considered as a series of barriers to mass transfer. From the perspective of mass transfer, these barriers are defined as biomass seepage recalcitrance. In this review, the porous characteristics of biomass materials was introduced for proposing biomass seepage recalcitrance and then provide some strategies for breaking seepage recalcitrance.