We report on the synthesis and characterization of new crosslinked polymeric matrices functionalized with heterocycle-based dyes, showing enhanced second and third order nonlinear optical activities. The matrices are poly(amido-amine)s (PAAs), a family of synthetic polymers in which amido and tertiary amino groups are regularly arranged along the main backbone. Particularly mild reaction conditions, easy processability, and high chromophore loading obtained in the case of highly crosslinked samples make PAA matrices valuable alternatives to conventional high Tg thermoplastic polymers. We also report on the strategic role of the nature and composition of the PAA matrix in the protection from photodegradation of photochemically unstable dyes.