There exists only few documentation for CIaO, yet. CIaO was developed while working on a diploma thesis about symbolically executing CSP-specifications. This thesis is available for download and describes the implementation as well as the theoretical background. It also contains a short chapter about how to use CIaO.
Dahlweid, M., Schulze, U.:
Symbolic Execution of CSP Specifications.
Master thesis, Computer Science Department, University of Bremen.