Poly(phenylsilsesquioxane) (PPSQ) polymers that were obtained from different synthetic routes were comparatively studied. The polymers were characterized by infrared and solid-state Si-29 NMR spectroscopies. According to the results of X-ray diffraction and thermogravimetric analyses, the materials richest in silanol showed a less organized network and lower weight loss temperature. The morphology of the products was influenced by the preparation conditions. PPSQ, with a morphology rich in spherical particles, was achieved with an n-hexadecyltrimethylammonium bromide template in the reaction medium, whereas the morphology of this polymer obtained in the absence of the template was featureless. Small-angle X-ray scattering analyses revealed that the PPSQ samples showed a predominance of surface-fractal behavior.