Porous carbon nanofibers with unique hierarchical structures have great potential in many fields, including heterogeneous catalysis, optoelectronics, and sensing. However, several preparation issues, such as additional templates, complicated processes, and harsh conditions, seriously hamper their widespread use. Here, we control the Sonogashira coupling reaction of linear building monomers─1,4-dibromaphthalene and 1,4-ethylbenzene─at the molecular level. Due to the occurrence of branching chain reaction (side reaction), 1D oligomer expands the growth orientation in the plane direction, forming a curled 1D fiber polymer. After thermal-driven skeleton engineering, porous carbon nanofibers were obtained with hierarchical channels of macro- (150 nm), meso- (5.2 nm), and microcavities (0.5 and 1.3 nm). The integration of macro-/meso-/microporous structure reveals a fast and sufficient interaction with electrolyte molecules, facilitating the construction of high-performance electrical devices. Our strategy, using a side reaction to achieve the dimensionality control of 1D copolymerization, paves a new way for the facile preparation of porous carbon nanofibers.