The escalating environmental impact of oil pollution has necessitated the development of efficient and sustainable absorbent materials. Considering the large surface area and good flexibility of electrospun fibers, in this work, we aim to construct three-dimensional interconnected porous structures by using electrospun cellulose fibers as building blocks to allow highly efficient and repeatable oil absorption. Specifically, electrospun cellulose fibers were dispersed in water and assembled by covalently crosslinking, followed by a silanization process to improve the hydrophobicity of the fibrous matrices. The structure and properties of the assembled aerogels were studied by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, water contact angle (WCA) measurement, and compression test. All the aerogels exhibited multiscale morphological structures composed of major pores (up to 20 μm), minor pores (up to 1 μm), and semi-micron scaled fibers as the building blocks, and were capable of absorbing diversified oils and organic solvents owing to their three-dimensional interconnected porous structures (porosity > 93.5 %). In particular, Aerogel 1–1 exhibited exceptional oil absorption capacities (up to 37.82 g/g) and superior reusability as evidenced by the minimal changes in its absorption capacity and compressive strength after 20 absorption-compression cycles. Therefore, this work highlights the potential of the electrospun cellulose fiber-constructed aerogels for efficient oil pollution remediation and industrial wastewater treatment.