Troxerutin, a naturally occurring flavonoid glycoside, has a variety of beneficial activities characteristic for flavonols, such as strong antioxidant and anti-inflammatory properties. Besides the beneficial effects of troxerutin, limitations such as bioavailability have disrupted its application and prompt scientists to look for effective modification methods. This work presents the synthesis of troxerutin-based macromolecules with lipophilic poly(n-butyl acrylate) (PnBA) star arms via "core-first" procedure in a two-step synthetic route. Troxerutin as a polyphenol structure with ubiquitous reactive hydroxyl groups was for the first time modified with α-bromoisobutyryl bromide to receive an atom transfer radical polymerization (ATRP) initiator with 10 brominated initiation sites. The further step involved the synthesis of novel star-like macromolecules with troxerutin core and PnBA star arms by simplified electrochemically mediated ATRP (seATRP) in an environmentally friendly reaction medium-miniemulsion. Electrolysis under constant current conditions with temporal control was implemented, resulting in well-defined star-like polymers with complete preservation of chain-end functionality after restarting the synthesis. Hydrophobic properties of received troxerutin-based macromolecules were investigated by contact angles (Θ) measurements, followed by the free surface energy (FSE) calculations.