Spain overcame some nervous moments in the first half and blew out Ukraine for their second win of the EuroBasket Women in Liepaja.
Evaristo Perez's team prevailed 85-59 and will now take on undefeated Slovakia to determine the winner of Group A.
"We are delighted to have progressed to the next round with this win," said Spain's Alba Torrens, who had six points, pulled down five rebounds and dished out seven assists.
"We played a good game.
"Despite having a big lead, we continued to work and improve certain aspects of our game.
"Now we must think about tomorrow and try to finish first of our group."
Ukraine have now slumped to back-to-back defeats and will take on the Czech Republic in a battle for third place with a spot in the Qualifying Round the reward.
Spain threatened to deliver a first-quarter knockout after reeling off the game's first eight points with Anna Montanana pouring in four.
Ukraine tightened up on the defensive end and stormed back, knotting the contest a t 13-13 after an Ol'ga Dubrovina lay-up.
The game remained close until midway through the second quarter.
After Inna Kochubei knocked down a three-pointer to cut the Spain advantage to 20-19, the silver medalists from the EuroBasket in Italy two years ago took command.
Laura Nicholls made two free throws and then Anna Cruz intercepted a Kochubei pass and went in for a lay-up.
Spain would end up with an 8-0 run to lead 28-19 and with Ukraine trying to stay within striking distance, Isa Sanchez all but killed off their hopes.
The Halcon Avenida sharpshooter made a pair of free throws and also drilled a three-ball right before the buzzer for a 39-26 Spain lead.
Ukraine got no closer than 11 points the rest of the way.
"For us it was great to be able to keep up with Spain in the opening half," said Ukraine's Iryna Biryuk, who had a game-high 16 points in defeat.
"To have a chance to play against such a big team as Spain it's wonderful for us.
"This game was a good learning experience."
Silvia Dominguez scored all 11 of her points in the second half to lead Spain in scoring.
Cindy Lima, Lucila Pascua, Laura Nicholls, Laia Palau and Anna Montanana each had 10 points in a balanced Spanish scoring attack.
Spain outrebounded Ukraine 37-25 and they also forced Volodymyr Bryukhovetskyy's team to turn the ball over 22 times.