The effect of the chemical configuration of network segments on the physical properties, cure properties, mechanical performance, and chemical stability of polycyanurate networks was investigated via synthesis, network formation, and characterization of an isomeric series of n-propyl-bridged cyanate ester monomers. Configurations that provide cyanurate oxygen atoms with either nearby methyl groups or nearby bridge groups exhibited decreased moisture uptake by up to 50%, along with a roughly 20-40 degrees C reduction in the loss in glass transition temperatures due to hydrolysis, for networks immersed in 85 degrees C water for 96 h. In ortho,para-linked aryl cyanates, dry glass transition temperatures of cured networks were reduced compared to analogous para,para-linked networks, by only about 10 degrees C, compared to a reduction of 30 degrees C in ortho-methylated cyanate ester networks, leading to higher "wet" glass transition temperatures in the ortho,para-linked networks. Neither methyl groups nor bridge groups in a position ortho to the reactive cyanate ester groups prevented the creation of networks with >99% conversion at cure temperatures of 230 degrees C. Networks with placement of methyl groups in a position ortho to the cyanate ester exhibited char yields in nitrogen at 600 degrees C of 46-47% compared to 43% for networks with methyl groups in the corresponding meta position, regardless of whether a sterically hindered environment was present around the cyanurate oxygen. These results illustrate the manner in which the chemical configuration around reactive groups can substantially modify the properties of networks even when the number density and type of reactive-group present do not change.