Italy defeated Romania 76-60 in Taranto on Wednesday evening - the final night of the Additional Qualifying Tournament for both sides.
With Germany having already sealed first place in Group B and set up a two-legged Final with Group A winners Hungary, the Italians and Romania had only pride to play for.
Simona Ballardini paced the Italians with 18 points.
The Azzurre trailed 36-34 at half-time but their class told after the break when they outscored Romania 42-24 to take a 16-point win.
As hosts of Group B, the Italians had a great opportunity to claim the only spot on offer for the EuroBasket Women, which tips off in Poland in June 18.
Instead, they will have to console themselves with a 3-1 record - the same as pool winners Germany.
The Germans progressed because of their 78-57 blowout of Italy on Sunday.
Romania had some good moments the past several days but ended up with just one win in four games.