Colloidal lithography is a cost-efficient method to produce large-scale nanostructured arrays on surfaces. Typically, colloidal particles are assembled into hexagonal close-packed monolayers at liquid interfaces and deposited onto a solid substrate. Many applications, however, require non close-packed monolayers, which are more difficult to fabricate. Preassembly at the oil/water interface provides non close-packed colloidal assemblies but these are difficult to transfer to a solid substrate without compromising the ordering due to capillary forces acting upon drying. Alternatively, plasma etching can reduce a close-packed monolayer into a non close-packed arrangement, however, with limited interparticle distance and compromised particle shape. Here, we present a simple alternative approach toward non close-packed colloidal monolayers with tailored interparticle distance, high order, and retained spherical particle shape. We preassemble poly(N-isopropylacrylamide)-silica (SiO2@PNiPAm) coreshell particles at the air/water interface, transfer the interfacial spacer to a solid substrate, and use the polymer shell as a sacrificial layer that can be thermally removed to leave a non close-packed silica monolayer. The shell thickness, cross-linking density, and the phase behavior upon compression of these complex particles at the air/water interface provide parameters to precisely control the lattice spacing in these surface nanostructures. We achieve hexagonal non close-packed arrays of silica spheres with interparticle distances between 400 and 1280 nm, up to 8 times their diameter. The retained spherical shape is advantageous for surface nanostructuring, which we demonstrate by the fabrication of gold nanocrescent arrays via colloidal lithography and silicon nanopillar arrays via metal-assisted chemical etching.