AbstractColloidal particle formation followed by their clustering has been shown to be the normal way of ageing of aminoplastic resins, in particular melamine–urea–formaldehyde (MUF) resins. Ageing (or further advancement of the resin by other means such as longer condensation times) causes whitening of the resin. This is a macroscopic indication both of the formation of colloidal particles and of their clustering. Some clustering appears rather early in this process, even when the great majority of the resin does visually appear to be in colloidal state, being transparent. However, it eventually progresses to resins which are mostly in colloidal, clustered state, followed much later by a supercluster formation starting to involve the whole resin. There appears to be clear correspondence between molecular mass increases as obtained by gel permeation chromatography (GPC), low‐angle laser light scattering (LALLS) analysis, and observation by polarizing optical microscopy. LALLS, however, appears to indicate the dimensions of the colloidal particles themselves when the level of colloidal aggregation is rather low, but it indicates the dimensions of the clusters once these are mostly aggregated. The smaller visible colloidal particles, already aggregates, were found by polarizing optical microscopy to be of a mostly elongated, rodlike shape, the length of which was shown to grow much further than their width with resin advancement and ageing. As their dimensions indicate, these are already clusters; this implies that the mainly linear increase of the polycondensate chains influences also the simpler colloidal clusters' growth direction, possibly explaining the resins' lack of tridimensional hardening while still in storage. It also explains why molecules such as free urea and acetals, by disrupting these colloidal aggregation mechanisms, allow both a much longer shelf life of the resin and its better performance in hardening. These findings explained the considerable difference in the behavior and performance of different MUF resin formulations. The ageing of the MUF resins of different preparation procedures appeared then to proceed from (1) clear resin (molecular colloidal aggregation) to (2) superclusters of a whitened, heavily thixotropic resin, which is the beginning of physical gelation to (3) liquid/cluster separation, which is the terminal stage of physical gelation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2690–2699, 2004