Negative ions Cl–, Cl2–, CCI–, CHCP–, and CCl2– are observed in vacuum-ultraviolet ion-pair photodissociations of chloroform (CCI3H) using the Hefei synchrotron radiation facility, and their ion production efficiency curves are recorded in the photon energy range of 10.00-21.50 eV. Two similar spectra of the isotope anions 35Cl– and 37Cl– indicate the following: Besides the strong bands corresponding to tbe electron transitions from valence to Rydberg orbitals converging to the ionic states, some additional peaks can be assigned with the energetically accessible multibody fragmentations; a distinct peak at photon energy 14.55 eV may be due to a cascade process (namely, the CI2 neutral fragment at the highly excited state D' 23Πg may be produced in the photo dissociation of CCl3H, and then the Cl– anions are produced in the pulsed-field induced ion-pair dissociations of Cl2 (D' 23Πg); two vibrational excitation progressions, nv2+ + v2++, and nv4++ and nv4+ + v2+, are observed around Č 2E and D 2E ionic states, respectively. The enthalpies of the multibody fragmentations to Cl2, CCI–, CHCl–, and CCl2–are calculated with the thermochemistry data available in the literature, and these multibody ion-pair dissociation pal production spectra. [ABSTRACT FROM AUTHOR]