It's all about the processing...
What you'll find in many cases of materials engineering is it's not what you make, but how you make it. Silicon semiconductors are usually fairly pure (if not completely pure) Silicon, which is a natural semi-conducting device because of its intrinsic electron configuration. I won't get into detail on why it's a semi-conductor, just know that in its natural state, Silicon (Si) has 4 valence electrons that can participate in conduction if given the right amount of initial energy (hence it's semi-conducting unlikle metals, which conduct all the time).
Silicon glass, which is actually SiO2 glass (usually with considerably more additions) is processed very differently. Glass is made by mixing raw materials (generally as powders) and then heating until the mixture is throughly melted. The melt is then cooled at a rate, which is fast enough to prevent the atoms from lining up in thier natural way. Scientifically we'd say the cooling rate must be sufficient that the thermodynamic forces of cooling counter the kenetic force of the atoms trying to align in a crystal structure. This means the cooled glass has a much different atomic structure from it's crystalline counterpart. Because of this, those electrons in Silicon are no longer available for energy absorption and the glass is not only an electrical insulator but is transparent.
At the end of the day, most all physical/mechanical properties are determined by bonding and the resulting electron configurations. Because crystalline Si and non-crystalline (amorphous) SiO2 have significantly different bonding/ electron configurations, their mechanical, optical, and electrical properties are much different