Poly(arylazophosphonate)s are synthesized from bifunctional diazonium salts and bifunctional phosphoric diesters by interfacial polycondensation at the interface water/organic solvent. The azo unit is formed via N-P coupling during the polycondensation reaction in satisfying yield and selectivity. Fifteen new polymers were synthesized and characterized by common methods such as 1H, 13C, and 31P NMR, FTIR, UV/visible spectroscopy, and DSC and GPC measurements. According to first laser ablation experiments as well as film forming properties and thermal and photochemical behavior, poly(arylazophosphonate)s seem to be suitable materials for ablation with XeCl excimer lasers.