studied as promising surfactants for emulsions. [10] Furthermore, vinyl-terminated polyglycerols were used as surfmers to synthesize stable polystyrene (PS) microspheres for medical diagnostics for possible postfunctionalization with proteins. [11,12] Hyperbranched and linear surfmers based on polyglycerols were additionally used to generate stable PS nanoparticles. [13] However, for the miniemulsion approach only less multifunctional PG-based surfactants or surfmers are known.Here, we use the versatility of the anionic polymerization of glycidyl ethers to prepare a series of multifunctional (additional OH-groups or polymerizable CC-groups) surfactants with adjustable hydrophiliclipophilic balance (HLB) that allows the stabilization of direct (oil-in-water) or inverse (water-in-oil) (mini)emulsions or can be used simultaneously for both systems.Two known orthogonal protection strategies, reported by Möller and coworkers, [14] were used to synthesize linear completely poly glycerol-based block copolymers as surfactants or surfmers for direct, inverse, or both types of miniemulsions (Scheme 1). The orthogonal-protected block copolymers were generated by anionic ring-opening polymerization in bulk using ethoxyethyl glycidyl ether (EEGE) and allyl glycidyl ether (AGE) or tert-butyl glycidyl ether (tBuGE) with defined block length ratios to tune their HLB. After acidic hydrolysis of the acetal groups, the water-soluble allyl-functionalized PG block copolymers were established as surfmers in the radical miniemulsion poly merization of styrene to generate polystyrene nanoparticles with decreased protein adsorption behavior due to incorporated PG surfactants (Scheme 1). In addition, oil-soluble allyl-functionalized block copolymers were introduced as surfmers to produce polyurea/urethane nanocapsules by interfacial polyaddition reactions of hydroxyethyl starch (HES) with toluene diisocyanate (TDI) (Scheme 1). [15] Furthermore, the allyl-protection groups on the polyurethane nanocarrier surface were utilized for surface functionalization by thiol-ene addition in water. For this purpose, the nanocarriers were transferred into water including a tert-butyl-protected poly glycerol block copoly mer. The tert-butyl-protected polyglycerol block copolymers were applied as surfactant to generate polystyrene nanoparticles in direct miniemulsions for comparison with the allyl-protected surfmer and in inverse miniemulsions to produce stable poly(hydroxyethyl methacrylate) (PHEMA)