Electrospinning is used to control the interface structure of macro‐polyacrylonitrile (PAN) fibers, and nano‐porous fibers (E‐PAN) which possess enhanced adhesion and interface effects. Herein, E‐PAN was prepared via electrospinning and was in turn incorporated into styrene‐butadiene‐styrene (SBS) asphalt to prepare PAN modified asphalt. The effect of E‐PAN addition on the performance of modified asphalt was explored. Fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction, scanning electron microscopy, atomic force microscopy (AFM), and AFM tests confirmed that E‐PAN exhibited a highly rough nano‐porous skeleton without any prominent structural damage during the preparation process. The three major indexes, dynamic shearing rheometer, MSCR, rotational viscosity, and thermogravimetric analysis tests results showed that E‐PAN modified asphalt exhibited excellent viscoelasticity, anti‐rutting and anti‐fatigue properties and thermal stability (THRI of 192.7°C). FT‐IR test of the four components of modified asphalt confirmed that E‐PAN chemically crosslinked with the saturates and aromatics in the base asphalt and SBS, which resulted in a uniform and well‐developed network structure. In addition, Brauner‐Emmett‐Teller and fluorescence microscopy results confirmed that E‐PAN got fully swollen in a behavior similar to that of SBS in the base asphalt, and hence helped SBS to form an excellent network structure in asphalt. E‐PAN played the important role of stress buffer, mutual entanglement, and good thermal insulation inside the asphalt.