Content originally posted in LPCWare by gbm on Fri Jan 13 04:13:42 MST 2012
They are not ESD protection diodes. They are ordinary diodes with specified maximum current guaranteed not to cause latchup. They may be used safely if the maximum allowed current is not exceeded.
There are, however, some quirks. First, many manufacturers do not specify the max. current. Second, in 3.3 V powered 5 V IO tolerant devices, the structure of IO pad may be not that obvious - this affects the positive voltage clipping.