The microgelation phenomenon during the curing of unsaturated polyester resin was investigated by both static and dynamic light scattering before gelation. The results of static light scattering revealed that the polymer molecular weight increased with degree of curing. The second virial coefficient, A(2), decreased slowly in the initial stage of curing and decreased dramatically at a conversion around alpha similar to 8.7%, indicating a drastic decrease of compatibility between the polyesters and styrene. Two modes of the size distribution of the microgel particles during curing were observed by dynamic light scattering. The small particles consist of primary unsaturated polyester molecules. The large ones consist of microgel particles formed by linking adjacent polyester molecules. The sizes of the microgel particles increased in the initial stage of curing, then decreased slightly at a conversion of alpha similar to 8.7%, which was due to the intramolecular crosslink reaction of the microgel particles. The experimental results revealed that the compatibility between polyesters and the styrene monomer became worse as the intramolecular crosslinking reaction inside the microgel particles caused a tight packing of the micro-gel molecules.