This study investigates carbon, hydrogen, nitrogen and chlorine isotope fractionation during the transformation of 3-chloroaniline (3-CA) via direct photolysis, TiO2 photocatalytic degradation at neutral condition and hydrolysis at pH 3, pH 7 and pH 11. Direct photolysis and ∙OH reaction (UV/H2O2) showed similar inverse isotope fractionation (ε) for carbon (1.9 ± 0.4 ‰ and 1.9 ± 0.6 ‰), for hydrogen (6.9 ± 1.6 ‰ and 5.0 ± 2.6 ‰), and inverse chlorine (13.9 ± 3.8 ‰ and 11.9 ± 2.9 ‰) and no nitrogen isotope fractionation, respectively. In contrast, significantly different normal carbon (-0.5 ± 0.1 ‰), inverse hydrogen (6.6 ± 1.5 ‰), and normal nitrogen (-0.8 ± 0.2 ‰) and inverse chlorine (5.2 ± 3.7 ‰) isotope fractionations were observed for the photocatalysis of 3-CA by TiO2 indicating a different degradation pathway as expected from ∙OH. For hydrolysis, inverse carbon (0.7 ± 0.3 ‰) and hydrogen (12.5 ± 3.3 ‰) isotope fractionation have been found at pH 3 while a normal carbon isotope fractionation was observed at pH 7 (-0.9 ± 0.3 ‰) and pH 11 (-1.3 ± 0.4 ‰), respectively. The correlation of 2H and 13C, 15N and 13C, and 37Cl and 13C isotope fractionation (Λ) allowed to distinguish direct photodegradation (ΛHC = -4.6 ± 1.7 (ΛHC-YORK=-5.2 ± 1.0) and ΛCl-C = 8.7 ± 0.9 (ΛCl-C-YORK=8.0 ± 0.3)), UV/H2O2 oxidation (ΛHC = -4.7 ± 1.0 (ΛHC-YORK=-4.5 ± 0.6) and ΛCl-C = 6.7 ± 0.8 (ΛCl-C-YORK=7.0 ± 1.0)), UV/TiO2 photocatalysis (ΛHC = -9.2 ± 3.1 (ΛHC-YORK=-9.3 ± 1.4), ΛCl-C = -10.2 ± 1.5 (ΛCl-C-YORK=-12.4 ± 1.7) and ΛNC -2.2 ± 0.3 (ΛNC-YORK=-2.3 ± 0.4)) and the modes of hydrolysis (ΛHC = 15.2 ± 5.3 (ΛHC-YORK=17.9 ± 2.9) and ΛCl-C = 0.9 ± 0.2 (ΛCl-C-YORK=1.1 ± 0.1) at pH 3) of 3-CA. The results were mechanistically interpreted highlighting the potential of CSIA to elucidate chemical oxidation and hydrolysis mechanisms of 3-CA.