The aim of this work was to examine the influence of polycaprolactone (PCL) as a soft segment (SS) on the surface properties of polyurethane networks (PUNs). Five PUNs with different SS content (from 10 to 50 wt%) were prepared using Boltorn® aliphatic hyperbranched polyester of the second pseudo generation and isophorone diisocyanate as components of hard segments. The structure, hydrophobicity, wettability, and swelling behavior of these PUNs were investigated. Primarily, the obtained results showed that properties of prepared PUNs strongly depend on the content of SS that is, PCL. It has been established that the increase of SS content reduced the degree of hydrogen bonding in PUNs. Also, the increase of the SS content in PUNs induced appearance of more pronounced microphase separated morphology, better hydrophobicity and non‐wetting with diiodomethane. Simultaneously, the increase of the SS content led to the decrease of contact angles with formamide, and surface free energy of the prepared PUNs. These PUNs show good surface properties that are required for their potential application such as coatings.