Novel mesoporous silica nanoparticles of peculiar shapes were synthesized, from which hierarchically porous silica coatings were fabricated on glass substrates via layer-by-layer (LbL) assembly, followed by calcination. These porous silica coatings were highly transparent and superhydrophilic. The maximum transmittance reached as high as 94%, whereas that of the glass substrate is 91%. The time for a droplet to spread lower than 5 degrees decreased to as short as 0.25 s. After the coating surface was treated with a low surface energy material, the surface became superhydrophobic (water contract angle >150 degrees) with a very low sliding angle of <1 degree. Compared with MCM-41-type mesoporous silica nanoparticles, the coatings fabricated using the novel mesoporous silica nanoparticles possess much better self-cleaning property. We used scanning (SEM) and transmission (TEM) electron microscopy to observe the morphology and structure of nanoparticles and surfaces. Transmission spectra and their change with time were characterized by UV-vis spectrophotometer. We studied the surface wettability by a contact angle/interface system. The influence of mesopores on the transmittance and wetting properties of coatings was discussed on the basis of experimental observations.