When did DECNET first appear?
Mid-1970s, depending on which version ("Phase") you consider to be
"DECnet". I'm sure someone will provide a more specific date.
using what means to connect each system.
Point to point serial (note that doesn't mean RS-232!) links (rarely
parallel) using various means for the actual physical connection.
DECnet definitely predates Ethernet by many years, if that's your point.
Bob
ANF10!