The 26-year-old replaces Arjen Robben as skipper after the Bayern Munich winger retired from international football in October.
"To be named captain of Holland is something very special," Van Dijk told a news conference on Thursday. "I hope I can keep going and get better every day."
The imposing centre-back will lead a new look Dutch side in Koeman's first game as the Dutch seek to put the disappointment of failing to qualify for this year's World Cup behind them.
Van Dijk will come up against several Liverpool team mates in the friendly in Amsterdam on Friday, including club captain Jordan Henderson, fellow defender Joe Gomez and midfielders Alex Oxlade-Chamberlain and Adam Lallana.
"It is going to be a special game," Van Dijk added. "It's a big start for us, a sort of a restart and we have to show what we have been working on."
(Reporting by Shrivathsa Sridhar in Bengaluru, editing by Ed Osmond)
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