Macroporous carbon nanofibers with mesoscale surface openings were produced by electrospinning. During the electrospinning of polyacrylonitrile ( PAN) solution including crosslinked polymer colloids, the polymer colloids were concentrated in the center of PAN fibers. Carbonization left interconnected spherical pores inside the carbon fibers and mesoscale openings in the fiber surfaces. The existence of surface openings facilitated inward diffusion of various solvent molecules, nanoparticles, and large molecules such as proteins. The porous fibers could be dispersed in both hydrophilic and hydrophobic solvents and materials, which enabled production of polymer composites in which the fibers and polymers were interpenetrating through the pores. Silica coating on the macroporous carbon fibers enriched the surface chemistry to effectively immobilize proteins helped by easy diffusion through surface openings.