This contribution describes the synthesis and properties of three classes of model NLO chromophore-functionalized high-Tg polymers which test current ideas about architecture-Tg- χ(2) performance relationships. Condensation of bismaleimides with diallylamino-functionalized donor-acceptor chromophores yields polable matrices with Tg values as high as 325°C and χ(2) responses as high as 0.7 × 10-7 esu (27 pm/V; λohigh as 0.7 × 10-7 esu (27 pm/V; λo = 1064 nm; 1.17 eV). Likewise, = 1064 nm; 1.17 eV). Likewise, condensation of o,o'-diallylbisphenol A with bismaleimides followed by chromophore functionalization yields an analogous series of polyimides with Tg values as high as 260°C and χ(2) response as high as 1.0 × 10-7 esu (42 pm/V at λo = 1064 nm). Polymerization of a bis(4-aminophenyl)lophine chromophore with bismaleimides or diisocyanates yields polymers with Tg values as high as 350°C and χ(2) = 0.62 × 10-7 esu (25 pm/V at λo = 1064 nm). All members of the above series exhibit minor to negligible decay in χ(2) response on aging in air at 100°C for 1000 h. The lophine-based material exhibits only ∼10% χ(2) decay on aging for 100 h at 200 °C under N2.