Formation of layered nanosheets and micro-spheres from a simple self-assembly and polycondensation of n-octadecylsilane (PODS) in water and toluene is demonstrated, respectively. The structure of the micro-spheres was characterized by Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD). According to the TEM images, it was firstly confirmed that the micro-spheres consist of stacks of bilayered polymerized n-octadecylsilane with head-to-head arrangements. The co-effects of water and solvent were proposed to control the octadecyltrichlsilane hydrolysis process and eventually the morphology of the micro-spheres. A micelle formation mechanism for the formation of the PODS micro-spheres under the co-effects of water and solvent were firstly proposed.