The anionic and cationic photodissociation from deep-core excited chloroform molecule has been investigated in the vicinity of the Cl 1s excitation edge. We used synchrotron radiation, time of flight mass spectrometry and ion yield spectroscopy. From our partial anion yield results we were able to observe for the first time the formation of the following anionic species: Cl-, H- and C-. From our TOF spectra we determined the cations produced in order to discuss the photoionization and dissociation dynamics for this core excited molecule. It provided evidences of the complex dynamics of negative and positive ion formation from CHCl3 upon photo-excitation in the vicinity of the Cl 1s edge. (C) 2012 Elsevier B.V. All rights reserved.