High silica glass is formed by sintering a dried gel. The gel has a pore size distribution such that at most about 5% of the total pore volume is contributed by pores having an effective pore diameter greater than about 0.5 .mu.m, and such that at least 10% of the total pore volume is contributed by pores having an effective pore diameter greater than about 0.02 .mu.m. This pore size distribution permits effective migration of fluid into, and out of, the gel, permits sintering at a lower temperature, and results in increased perfection of the glass. The pore size distribution can be achieved by appropriate comminution, e.g., ball-milling, of intermediate material. A novel process for forming high silica glass is also disclosed. The process comprises forming intermediate material by hydrolysis of one or more metal alkoxides, comminuting the intermediate material to produce colloidal particles, forming a sol by dispersing the particles in liquid, gelling the sol, drying the gel, and sintering the dried gel.