Heterogeneous catalysis plays a pivotal role in the current chemical and energy vectors production. Notably, to fully utilize the intrinsic activity and selectivity of a catalyst, the chemical reactor has to be designed and operated optimally to achieve enhanced heat/mass transfer, well-defined contact time of reactants, uniform flow pattern, and high permeability. Structured catalysts are a promising strategy to overcome the major drawbacks encountered in the traditional packed-bed reactor technology due to the improved hydrodynamics in combination with enhanced heat/mass transfer. Newly emerged fiber/foam-substrates, with an entirely open 3D network structure, bring distinct advantages over the honeycomb and micro-channel contacting methods, including free radial diffusion, eddy-mixing driven heat/mass transfer, large area-to-volume ratio, and high contacting efficiency. However, how to place the nanocatalysts onto the fiber/foam-substrates is a challenging problem because the commercial washcoating method has great limitations such as the nonuniformity and easy exfoliation of coatings. This review discusses the newly developed non-dip-coating methods for the fiber/foam-structured catalysts and their promising applications in the strongly exo-/endo-thermic and/or high throughput reaction processes.