The former Real Madrid and Inter Milan striker played against Brazil at the same stage of the tournament at the 1998 finals in France. The Brazilians won 4-1, Chile went home and Zamorano never got to play in a World Cup again.
Twelve years later he is back as a television commentator and thinks Marcelo Bielsa's side have a chance of avenging that defeat.
"I think Bielsa's boys are ready for anything," Zamorano told Reuters. "It all comes down to one match now, and it happened to me in France in 1998.
"We got to the last 16 and we faced Brazil at their best and it all ended for us there but you can always dream of going as far as possible."
Zamorano was part of a Chile squad that boasted two outstanding strikers - himself and Marcelo Salas - but was otherwise flawed. In contrast, the current squad has no big names but is generally much stronger.
EXCITING FOOTBALL
They finished second behind Brazil in the South American qualifying campaign and scored 32 goals in the process, winning a reputation for exciting football.
"We've got a good team," Zamorano said. "I think in general we've offered something different.
"I think Bielsa has stamped the Bielsa philosophy on the players and we've seen that reflected on the pitch. Chile are not interested in defending, the only thing that concerns them is attack."
Zamorano, who scored 34 goals for Chile in 69 appearances, said he was delighted to see South American teams doing so well at the World Cup.
"They've nearly all finished top of their groups and they're looking to play in a way that has something to do with the very identity of South American football," he said. "In general they've looked to take the game to the opposition."
He said his job as commentator was much more difficult than playing football but was glad to be back at football's flagship tournament.
"It was an amazing thing to be able to play at the World Cup in 1998 and now I'm enjoying it from the outside, and above all I'm enjoying what Chile are doing."
