ABSTRACTSmall angle x-ray scattering (SAXS) is the technique of choice for the determination of structure on the 10–1000Å scale. We have used this technique to study the growth and topology of the macromolecules which precede gelation in several chemical systems used in sol-gel glass technology. The results show that branched polymers, as opposed to colloids, are formed. The alcoholic silica system is akin to organic systems where gelation occurs through growth and crosslinking of chain molecules. Data are reported from both the Porod and Guinier regions of the SAXS curve and these data are interpreted in terms of geometrical structures predicted by various disorderly growth processes. The results indicate that the degree of crosslinking can be controlled by catalytic conditions. The degree of crosslinking may, in turn, control phase separation and processability to a dense glass.