The clinical need for vascular grafts is associated with cardiovascular diseases frequently leading to fatal outcomes. Artificial vessels based on bioresorbable polymers can replace the damaged vascular tissue or create a bypass path for blood flow while stimulating regeneration of a blood vessel in situ. However, the problem of proper conditions for the cells to grow on the vascular graft from the adventitia while maintaining its mechanical integrity of the luminal surface remains a challenge. In this work, we propose a two-stage technology for processing electrospun vascular graft from polycaprolactone, which consists of plasma treatment and subsequent immobilization of hyaluronic acid on its surface producing thin double-sided graft with one hydrophilic and one hydrophobic side. Plasma modification activates the polymer surfaces and produces a thin layer for linker-free immobilisation of bioactive molecules, thereby producing materials with unique properties. Proposed modification does not affect the morphology or mechanical properties of the graft and improves cell adhesion. The proposed approach can potentially be used for various biodegradable polymers such as polylactic acid, polyglycolide and their copolymers and blends, with a hydrophilic inner surface and a hydrophobic outer surface.