Hi,
First check these two thing in Pl/Sql developer:
Tools -> Preferences - > Options:
Check Oracle Home and OCI library is empty or not
It both are empty then,
set those two locations:
i.e
Oracle Home = C:\oracle\product\10.1.0\db_1\BIN
OCI Library = C:\oracle\product\10.1.0\db_1\BIN\oci.dll
These location may differ. For Oracle Home find BIN directory..For OCI Library find oci.dll location and set these two values and reopen the pl/sql developer 'll take tnsname file from the default location(i.e C:\oracle\product\10.1.0\db_1\NETWORK\ADMIN\tnsnames.ora).
The default location may differ just see ....NETWORK\ADMIN\tnsnames.ora path