As per datasheet the highest voltage on any pins on the PSoC device is same as the Vddios which have a limit of about 6V. The SIOs can tolerate upto 7V. But if you are expecting a protection for high voltage ESD that might be a different spec in the datasheet.
We use TRANSZORB for inputs that may have high voltage coming in. I would not just use the internal potection of the chip.
If the 100V DC which you are expecting is not ESD then it is necessary to protect the device from voltages above the specified maximum (Vmax).
One option would be to use isolators such as optocouplers.
Thank's to every one for the answers.
I will take into account the advices.