Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for the fabrication of a wide variety of nanoparticle arrays. We have previously shown that silica nanospheres (SNSs) 15 nm in diameter assemble into ring-like nanostructures in the presence of amphiphilic block copolymers poly[(2-ethoxyethyl vinyl ether)- block-(2-methoxyethyl vinyl ether)] (EOVE-MOVE) in an aqueous phase. Here, the effects of particle size of SNSs on this polymer-mediated self-assembly are studied systematically using scanning electron microscopy to observe SNSs of seven different sizes between 13 to 42 nm. SNSs of 13, 16, 19, and 21 nm in diameter assemble into nanorings in the presence of EOVE-MOVE. In contrast, larger SNSs of 26, 34, and 42 nm aggregate heavily, form chain-like networks, and remain dispersed, respectively, instead of forming ring-like nanostructures. The assembly trend for 26-42 nm-SNSs agrees with that expected from the increased colloidal stability for larger particles. Time-course observation for the assembled morphology of 16 nm-SNSs reveals that the nanorings, once formed, assemble further into network-like structures, as if the nanorings behave as building units for higher-order assembly. This indicates that the ring-like assembly is a fast process that can proceed onto random colloidal aggregation. Detailed analysis of nanoring structures revealed that the average number of SNSs comprising one ring decreased from 5.0 to 3.1 with increasing the SNS size from 13 to 21 nm. A change in the number of ring members was also observed when the length of EOVE-MOVE varied while the size of SNSs was fixed. Dynamic light scattering measurements and atomic force microscopy confirmed the SNSs/polymer composite structures. We hypothesize that a stable composite morphology may exist that is influenced by both the size of SNSs and the polymer molecular structures.