In this article, we show that introducing a N,N-dimethyl-formamide (DMF) solvent for silica nanosphere (SNS) monolayer spin-coating can offer a low-cost and simple spin-coating approach for SNS monolayer deposition even on large-area silicon surfaces. From our method, more than 95% monolayer coverage for a 2 in round Si surface was achieved, which is one of the highest reported coverage by a spin-coating method. We prove that DMF offers highly enhanced wettability and slow solvent evaporation rate compared to a conventional solvent, water, in addition to excellent SNS dispersibility in solution preventing SNS cluster deposition on the surface and consequently produces a close-packed SNS monolayer with good uniformity over the surface. In addition, the benefits of DMF are retained as the deposition area increases indicating its high tolerance to spin-coating area. Better than 90% SNS monolayer coverage on a 4 in Si substrate was achieved with the DMF spin-coating method. Moreover, DMF has the advantage that SNS spin-coating can be done under common ambient laboratory conditions with 100% pure DMF unlike previous approaches which require humidity and temperature controls or additional surfactant additions to the solution.