Carbon fibers have high surface areas and rich functionalities for interacting with ions, molecules, and particles. However, the control over their porosity remains challenging. Conventional syntheses rely on blending polyacrylonitrile with sacrificial additives, which macrophase-separate and result in poorly controlled pores after pyrolysis. Here, we use block copolymer microphase separation, a fundamentally disparate approach to synthesizing porous carbon fibers (PCFs) with well-controlled mesopores (10 nm) and micropores (0.5 nm). Without infiltrating any carbon precursors or dopants, poly(acrylonitrile--methyl methacrylate) is directly converted to nitrogen and oxygen dual-doped PCFs. Owing to the interconnected network and the highly optimal bimodal pores, PCFs exhibit substantially reduced ion transport resistance and an ultrahigh capacitance of 66 μF cm (6.6 times that of activated carbon). The approach of using block copolymer precursors revolutionizes the synthesis of PCFs. The advanced electrochemical properties signify that PCFs represent a new platform material for electrochemical energy storage.