Modern applications in biomedicine, drug delivery, and tissue engineering demand versatile materials capable of meeting multifaceted requirements. Conventional mono‐functional materials fall short of addressing these complex demands. To tackle this challenge, this study introduces an innovative approach utilizing bubble electrospinning for the fabrication of bipolymeric side‐by‐side nanofibers. These nanofibers incorporate distinct hydrophilic and hydrophobic domains aligned parallel to their axis, achieved through the electrospinning of polyvinyl alcohol (PVA) as the hydrophilic component, alongside either poly(ε‐caprolactone) (PCL) or Nylon6 as the hydrophobic component. The optimal diameter of the bubble electrospinning reservoir was theoretically determined via simulation of electric field using Maxwell 3D software and experimentally validated. Successful electrospinning resulted in nanofibers with hydrophilic and hydrophobic domains derived from PVA/Nylon6 and PVA/PCL polymer combinations. This innovative process yielded nanofibers with diameters as fine as 101 nm in the PVA/Nylon6 bipolymeric nanofibers. Transmission electron microscopy images provide compelling insights into the distinct interfaces formed during polymer‐polymer interactions within the nanofibers, manifesting the Janus structure. Furthermore, Fourier‐transform infrared spectroscopy confirms the presence of both polymers within the nanofiber matrix. This research represents a significant advancement in the efficient production of bipolymer nanofibers, holding promise for a wide range of applications.