Activists said they had also dug a tunnel under the hamlet in a bid to complicate the evacuation effort.
The movement has been supported by protest actions across Germany. On Friday, masked activists set fire to bins and painted slogans on the offices of the Greens in Berlin.
The party -- part of Germany's ruling coalition with Chancellor Olaf Scholz's Social Democrats and the liberal FDP -- has come under heavy criticism from activists who accuse it of betrayal.
Following the energy crisis set off by the Russian invasion of Ukraine, the government has brought old coal power plants back online.
Officials also signed a compromise deal with RWE that made way for the demolition of Luetzerath but spared five nearby villages.
The energy firm also agreed to stop producing electricity with coal in western Germany by 2030, eight years earlier than previously planned.