Phosphonates, commonly used as strong metal chelating agents in household and industrial products, partially persist through water treatment processes, releasing significant amounts into the environment and raise concerns about potential environmental impacts. This study investigated effects of pH-dependent speciation of phosphonates on their photolysis by a medium-pressure mercury lamp in aqueous solution under ambient air conditions. Different species of aminotrimethylphosphonic acid (ATMP), and its most important transformation products iminodimethylphosphonic acid(IDMP) and aminomethylphosphonic acid(AMPA) were analyzed by liquid chromatography in combination with isotope ratio (CSIA) and high resolution mass spectrometry. UV radiation (<320 nm) was required for the photolytic degradation of ATMP, IDMP, and AMPA, and their photolysis was influenced by pH-dependent speciation. Degradation rate constant of ATMP was affected by pH, but a direct correlation between kobs and pH was not found. In contrast, IDMP and AMPA exhibited a direct correlation between pH and kobs during photolysis. CSIA revealed an inverse carbon kinetic isotope effect (KIE) for ATMP, while a normal carbon KIE was observed for IDMP and AMPA. Quantum chemical calculations supported degradation pathway interpretation and KIE understanding. Energy barrier calculations distinguished N-C vs C-P bond cleavage, favoring N-C cleavage on average, consistent with observed transformation products. Further calculations, considering possible transition states, provide first promising hints for elucidation of present KIEs.