Phase change fibers (PCFs) can effectively store and release heat, improve energy efficiency, and provide a basis for a wide range of energy applications. Improving energy storage density and preserving flexibility are the primary issues in the efficient manufacture and application development of PCFs. Herein, we have successfully fabricated a suite of flexible PCFs with high energy storage density, which use hollow carbon fibers (HCFs) encapsulated phase change materials (PCMs) to provide efficient heat storage and release, thereby enhancing energy efficiency and underpinning a broad range of energy applications. The flexible HCF/LA PCFs with high energy density were made by impregnating a small molecule LA solution, whereas the precursor of the PAN/ZIF-67 composite fibers was created by electrospinning. These PCFs have a high loading capacity for lauric acid (LA), demonstrating a 92% load percentage and a 153 J g⁻¹ phase change enthalpy value. The effects of doping quantity (ZIF-67), fiber orientation, pre-oxidation treatment, and particle size on the morphological and structural characteristics of HCFs, as well as the impact of HCFs’ pore structure on PCM encapsulation, were investigated. It was found that the oriented fiber structure serves to reduce the likelihood of fracture and breakage of precursor fibers after carbonization, whilst the gradient pre-oxidation can maintain the original fiber morphology of the fibers after carbonization. These findings establish a solid theoretical foundation for the design and production of high-performance flexible porous carbon nanofiber wiping phase change composites.