Compound-specific isotope analysis was used to monitor the δ13C signature of chloroform produced upon the chlorination of model compounds representing natural organic matter functional groups (resorcinol, acetylacetone, acetophenone, phenol, and 2,4,6-trichlorophenol) and a natural water sample. For each model compound, a different apparent kinetic isotope effect was found for chloroform formation. Normal isotope effects were found for resorcinol, acetylacetone, and acetophenone, and ranged from 1.009 ± 0.002 to 1.024 ± 0.004. For the two phenols, an inverse effect was found (0.980 ± 0.004). Lake Zürich water also had a inverse effect (0.997 ± <0.001) indicating that phenols are likely chloroform precursors in NOM, but that other functional groups may also participate. The apparent 13C kinetic isotope effect for the addition/ elimination reaction of 1,1,1-trichloropropanone mediated by OH- to yield chloroform is 1.014 ± 0.002. A comparison of this value to those found for the chlorination of the model precursors and an evaluation of the differences in chloroform production kinetics for the different model precursors argue against a mechanism in which all NOM precursors react via a common intermediate. Compound specific isotope analysis may give additional insights into chloroform formation mechanisms beyond those allowed by current techniques.