Poly(L-lactide-co-succinic anhydride) networks were synthesised via the carbodiimide-mediated coupling of poly(L-lactide) (PLLA) star polymers. When 4-(dimethylamino)pyridine (DMAP) alone was used as the catalyst, gelation did not occur. However, when 4-(dimethylamino)pyridinium p-toluenesulfonate (DPTS), the salt of DMAP and p-toluenesulfonic acid (PTSA), was the catalyst, the networks obtained had gel fractions comparable to those which were reported for networks synthesised by conventional methods. Greater gel fractions and conversion of the prepolymer terminal hydroxyl groups were observed when the hydroxyl-terminated star prepolymers reacted with succinic anhydride in a one-pot procedure than when the hydroxyl-terminated star prepolymers reacted with presynthesised succinic-terminated star prepolymers. The thermal properties of the networks, glass transition temperature (T-g), melting temperature (T-m) and crystallinity (X-c) were all strongly influenced by the average molecular weights between the crosslinks ((M) over bar (c)). The network with the smallest (M) over bar (c) (1400 g/mol) was amorphous and had a Tg of 59 C while the network with the largest (M) over bar (c) (7800 g/mol) was 15% crystalline and had a T-g of 56 degrees C. (C) 2010 Elsevier Ltd. All rights reserved.