In recent years extensive efforts have been made to use multifunctional carboxylic acids as formaldehyde-free crosslinking agents for cotton to replace the traditional formaldehyde-based N-methylol reagents. In our previous research we found that a polycarboxylic acid esterifies cellulose through the formation of a five-membered cyclic anhydride intermediate by dehydration of two adjacent carboxyl groups. In this research we used Fourier transform IR (FTIR) spectroscopy to study the formation of cyclic anhydride intermediates and crosslinking of cotton by 1,2,4-butanetricarboxylic acid (BTA) and 1,2,3-propanetricarboxylic acid (PCA). BTA and PCA farm five-membered cyclic anhydrides in the same temperature range. Both acids form the anhydrides at lower temperatures when a catalyst is present. When an acid molecule is bonded to cotton through an ester linkage, only PCA is able to form a second anhydride intermediate. We found that PCA is a more effective crosslinking agent, and it imparts higher levels of wrinkle resistance to the cotton fabric than BTA. Therefore, the formation of a five-membered cyclic anhydride by a polycarboxylic acid accelerates the esterification of cotton by the acid.