"It is time to take control of our own destiny," the Hall of Famer said in a statement issued by the team Thursday.
The Penguins are free to move when the 2006-07 season ends following a state panel's rejection Wednesday of a casino company's offer to build the team a new arena for free.
Lemieux said talks will begin shortly with state and local leaders about a new arena, but added a move outside Pennsylvania is another option.
"Accordingly, starting today, the team is off the market," Lemieux said, "and we will begin to explore relocation offers in cities outside Pennsylvania."
Among the cities known to be interested in the Penguins are Kansas City, Houston, Portland, Ore., and Winnipeg.
The Penguins, who have sought a new arena since Lemieux's group brought the team out of bankruptcy in 1999, have had two major setbacks in the last week.
Last Friday, Canadian businessman Jim Balsillie stunned the Penguins and the NHL by pulling out of an estimated US$175-million agreement to buy the team. Balsillie was expected to close on the deal last week, only to back out after the NHL insisted he agree contractually to not move the team.
On Wednesday, a state gaming panel awarded the single licence to build a Pittsburgh slot-machine parlour to Detroit-based gambling company owner Don Barden rather than a Penguins-supported gaming concern. Isle of Capri Casinos promised to build a $290-million arena for the Penguins next door to its casino if it was granted the slots license.
While Isle of Capri could appeal the gaming board's decision, overturning the award could prove difficult because of language built into the state gaming law designed to prevent lengthy delays once the licences were awarded.
Within an hour of the slots announcement, state, county and city leaders rushed to assuage the Penguins, promising to start talks immediately on a so-called Plan B agreement to build the arena. A site has already been secured, and the Barden group has pledged $7.5 million a year for 30 years to help fund the arena. The state also would kick in $7 million.
Allegheny County Chief executive Dan Onorato and Pittsburgh mayor Luke Ravenstahl said they were ready to negotiate an arena deal immediately and were certain an agreement could be reached.
However, the Penguins would have to contribute money to the Plan B deal - something they weren't required to do by Isle of Capri.
Lemieux, exasperated the Penguins still don't have a replacement for 45-year-old Mellon Arena, warned Monday that there would be considerable uncertainty if Plan B became the only option. But, until now, he has not actively sought offers from other cities.
"I'm not sure about Plan B," Lemieux said. "Plan B, in my opinion, is going to use taxpayers' money. I've never heard of a government turning down $290 million in private money to build a public facility. It's unheard of. At this point, frankly, I'm really not sure of what's going to come of it."
While the Penguins were discouraged by Isle of Capri's failure to obtain the slots licence, they are now in position to negotiate a more favourable arena agreement.
Lemieux can use relocation as a powerful bargaining chip, and thus apply even more pressure on government officials to reach a deal quickly. Privately, executives with Lemieux's group have said the team would relocate only if it became certain there would be no new arena.
NHL commissioner Gary Bettman met recently in Pittsburgh with Onorato and Ravenstahl, presumably to discuss how Plan B would work if Isle of Capri wasn't chosen.
Despite the Penguins' longstanding arena issues, Pittsburgh remains one of the NHL's strongest U.S. markets. The Penguins, who have no NBA team in town to draw away attention and fans, played to 92 per cent of arena capacity last season, despite their fourth consecutive last-place finish.
Ticket sales are very strong for the rest of this season. TV ratings also are among the highest of any U.S. city.
Bettman's desire to keep the Penguins in Pittsburgh is one reason he wouldn't allow the sale to go through without strong contract language that prevented Balsillie from moving the team.
Pittsburgh's other two major sports teams, the Steelers and Pirates, also gained their new stadiums in 2001 following similar Plan B negotiations with political leaders. The original plan to fund the stadiums through a county sales tax hike was overwhelmingly rejected by voters.