A new class of high temperature polymeric materials capable of second order nonlinear optical effects has been developed and characterized. These polymers, Bisphenol A-poly (arylene ether) phosphine oxides (Bis A-PEPO), F6 Bis A-PEPO, phenolphthalein•PEPO (PP-PEPO), and phenolphthaIein-anilide•PEPO (PP-PEPO), doped with nonlinear optical chromophores are being examined using second harmonic generation. Corona poling is used to orient the chromophores into the noncentrosymmetric structure required to obtain the second harmonic signal. These high glass transition temperature (>200°C) polymers have strong hydrogen bonding sites that can interact with the chromophores. This work describes the basic polymer physics including local Mobility, chromophore/polymer interactions, and polymer steric effects that control the thermal and temporal stability of chromophore orientation in these guest-host polymeric systems.