Fourteen people were in the hotel in Kroev when one storey of the building collapsed late on Tuesday.
Five were able to get out of the building unhurt because they were not in the part that collapsed, police said, but others were trapped.
Rescuers were able to contact some of them by mobile phone.
But getting to them proved to be difficult because the collapse of one storey left two ceilings lying on top of each other, according to Joerg Teusch, fire and disaster protection inspector for the Bernkastel-Wittlich district.
"We have to proceed with caution because the entire building structure is like a house of cards," he said.
Fourteen people were in the hotel in Kroev when one storey of the hotel in Kroev collapsed. (AP PHOTO)
"If we pull on the wrong card, this building is sure to collapse."
Six people were rescued on Wednesday, and by mid-afternoon only one person was still trapped.
Emergency services were in contact with the remaining person and hoped to rescue them by sunset.
Among the first to be saved was a two-year-old child pulled out unharmed and the child's mother, who was rescued with minor injuries.
The child's father was rescued later.
"The whole story has a very emotional component because when we arrived, when we looked at the building, it looked like we weren't taking anyone out," Teusch said at a news conference.
The cause of the structural collapse has not been determined.
The original hotel building was believed to date to the 17th century, but additional storeys were added about 1980, Teusch said.
Building work had taken place on Tuesday, but it was not clear whether there was a link between that and the collapse.
Regional public broadcaster SWR said witnesses reported hearing a bang and seeing a large cloud of dust at the time of the collapse.
The rescue operation involved 250 emergency workers, including drone specialists, as well as rescue dogs.
Authorities evacuated 21 people from three buildings immediately around the damaged hotel.
The hotel guests at the time of the collapse were largely German, apart from a Dutch family.
Two Germans, a man and a woman, died.
Kroev is on a picturesque section of the river Moselle near the larger resort town of Traben-Trarbach.