A floor of the hotel in Kröv, in Rhineland-Palatinate, collapsed for unknown reasons shortly before 11 am on Tuesday, police said in a statement.
A woman and a man were killed in the accident, police spokesman Joerg Teusch told journalists on Wednesday.
Of the 14 people inside at the time, five managed to get out.
READ ALSO: What we know so far about fatal hotel collapse in western Germany
Seven others were rescued alive over the course the day, with the final person being pulled out late Wednesday "thanks to the tireless efforts of the rescuers", police said in a statement.
One man, a child and two women were the first to be rescued with minor injuries earlier in the day.
The rescue operation was difficult "as the building could only be entered... with the utmost caution", police said.
But by mid-afternoon two more people had been rescued, leaving just one person still trapped inside.
A total of 21 residents from the local neighbourhood were evacuated and some 250 search-and-rescue staff were working at the site.
The Moselle valley, which encompasses parts of Germany, France and Luxembourg, is a popular holiday spot with picturesque vineyards and traditional taverns.
The basic structure of the hotel was built in the 17th century, according to police, but two-and-a-half storeys were added in the 1980s.
An investigation into the cause of the collapse had been launched, public prosecutor Peter Fritzen said in Kroev.
Autopsies on the deceased were also being carried out. Details on the identities of the victims have not yet been released.
Interior Minister Nancy Faeser called images of the collapse "shocking".
"My sympathies and thoughts go out to the families of those killed," she said, wishing those injured a speedy recovery.
Dutch media reported that a family of three from Urk, a small fishing town in the north of the Netherlands, was among those caught up in the incident.
The mother and child were reportedly pulled out alive in the morning and the father rescued later in the day.
The woman was named as 23-year-old Edi Hoefnagel-Visser, a journalist with Het Urkerland local newspaper.
Her husband Mark Hoefnagel, 26, was "seriously injured" in the accident, according to Dutch public broadcaster NOS.
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