In recycling and reusing construction waste, carbonation of recycled concrete fine (RCF) has been successfully applied to produce value-added products, such as silica nanoparticles, via the breaking of calcium silicate hydrate (C-S-H) structure and condensation of silicate chains. However, the intricacies of carbonation of RCF with varying calcium to silicon (C/S) ratios and their implications on the size of generated silica nanoparticles remain unknown. In this work, we developed an optimized carbonation method at high water to solid ratio to fabricate silica nanoparticles from C-S-H with different C/S ratios. The particle size of silica nanoparticles was found to gradually decrease with the increased C/S ratio of C-S-H. Since as C/S ratio increased, silicate in Q state shifted to Q state and the silicate chain became shorter, shifting from long-range, disordered to short-range, ordered. As the disordered self-seeding growth of long silicate chains derived from C-S-H continued, the Si-O-Si network of silica nanoparticles became chaotic, leaving more unreacted Si-OH on its surface. On the contrary, the short silicate chains displayed higher possibility of condensation, making nanoparticles with a smaller diameter.