The defined assembly of nanoparticles (NPs) in polymer matrices is an important prerequisite for nextgeneration functional materials.Apromising approacht o control NP positions in polymer matrices at the nanometer scale is the use of blockc opolymers.I ta llows the selective deposition of NPs in nanodomains,b ut the final defined and ordered positioning of the NPs within the domains has not been possible.T his can nowb ea chieved by coating NPs with blockc opolymers.T he self-assembly of blockc opolymercoated NPs directly leads to ordered microdomains containing ordered NP arrays with exactly one NP per unit cell. By variation of the grafting density,the inter-nanoparticle distance can be controlled from direct NP surface contact to surface separations of several nanometers,determined by the thickness of the polymer shell. The method can be applied to aw ide variety of blockc opolymers and NPs and is thus suitable for abroad range of applications.The defined assembly of functional nanoparticles in polymer matrices is highly desirable for the development of nextgeneration electrical, optical, memory,and energy conversion devices. [1] Currently,t he lack of ap recise control of nanoparticle positions,d istances,a nd ordering in polymeric matrices is as evere barrier for many nanotechnology applications as these parameters sensibly determine mechanical, dielectric, magnetic, and plasmonic coupling as well as energy transfer in the active polymer matrices of the corresponding devices.Aversatile method to control nanoparticle locations and arrangements at the nanometer scale is the use of block copolymers. [2] ForABdiblock copolymers,nanoparticles can be selectively integrated into the AorBdomains,orinto the A/B interface. [3] Early studies aiming at ad omain selective integration involved either the synthesis of nanoparticles from precursors solubilized in the respective block copolymer domains,o ru sed pre-synthesized nanoparticles. [4] Later improved methods employed nanoparticles which were surface compatibilized with the targeted polymer domain.However,t he controlled and stable incorporation of inorganic nanoparticles into polymer matrices remains difficult, because nanoparticles are thermodynamically immiscible with polymers.This is due to 1) unfavorable nanoparticle/ polymer enthalpic interactions,a nd 2) ac onsiderable loss of conformational entropy when polymer chains are located close to the nanoparticle surface. [5] Theenthalpic interactions can be minimized by nanoparticle surface compatibilization with either polymer-compatible small molecules [6] or with polymers of the same type as the targeted block copolymer domain. As the conformational entropy of block copolymer chains is already reduced owing to their confinement at the domain interface,a dditional entropy losses owing to nanodomain incorporation immediately lead to problems of macrophase separation already at small volume fractions of nanoparticles. [7] By using small molecules with attractive interactions such as hydrogen bonding [8] and ioni...