Inspired by the recent developments in the controlled synthesis of porous materials, we present herein the structural prediction of silica nanoarchitectures by using the three- (3MRs) and four-membered rings (4MRs), which are more frequently found in the nanometer-sized particles than in the bulk form, as building blocks. The proposed models include the active molecular rings, thin nanowires, hollow nanotubes, discrete fullerene-like cages, and porous zeolite-like three- dimensional networks. Their geometrical and electronic structures and properties were studied by performing density functional calculations. These silica nanostructures were proved, using molecular dynamics simulations, to possess intrinsic structural stabilities with highly symmetrical geometries and regular nanochannels. These atomically well-defined clusters, (SiO)(n), are chemically more reactive than those proposed earlier and are energetically more favorable for n > 20 in high-level density functional calculations over the corresponding two-membered ring (2MR) chains and rings as well as the pure 3MR networks. The nanoparticles and nanodevices based on them are expected to have potential technological applications that mainly make use of their characteristic geometrical structures (nanosized pores) and novel electronic properties.