Let me divide the question into 2 parts.
1. Why do birds sit on high power voltage lines ???
We all have observed that the birds usually sit on single line of high power voltage lines.
Reason is very simple.
The wires offer a nice perch from which birds can view their surroundings for potential predators or prey with their views undisturbed by foliage of trees !!!!
2. Why they are not electrocuted ???
Birds sitting on a single power line are not electrocuted because they are not grounded.
Such birds are not forming a connection between the power line and ground. So they are not completing the electric circuit.
If the bird touches 2 wires simultaneously, it provides an easy path to electricity to flow to ground through it.
At this time, electric circuit becomes complete and birds get electrocuted.
Usually big birds or birds with large wings easily get electrocuted whereas small birds sitting on a single line don't.