World number one Netherlands, who are seeking a third successive gold, beat Argentina 3-2 in the quarter-finals, while Germany dumped out the United States with a 2-1 victory on Monday.
New Zealand hammered world number three Australia 4-2 in their quarter-final to set up a chance of a rare hockey medal, as Britain, who won the bronze medal in the 2012 London Games, ousted Spain 3-1.
Netherlands were quick off the blocks against world number two Argentina as they romped to a two-goal lead thanks to goals from Laurien Leurink and Lidewij Welten in the first half.
Kelly Jonker opened up a three-goal gap after she scored from a penalty corner just six minutes into the third quarter but Argentina's Florencia Habif pulled one back ahead of the final quarter.
Delfina Merino scored eight minutes from the final whistle to set up a nervy ending but Netherlands nullified Argentina's attacking threat to book their place in the final-four.
Germany held off a late surge by the United States to advance to the semi-final. Germany's Marie Mavers opened the scoring with a goal midway through the first period.
Lisa Altenburg knocked in a backhanded shot high over U.S. goalkeeper Jackie Briggs to put Germany up 2-0 late in the first.
Katelyn Falgowski's goal with four minutes left gave the Americans a glimmer of hope, but the Germans remained strong defensively to set up a semi-final clash with Netherlands.
New Zealand took an early lead as Anita McLaren converted a penalty corner and Kelsey Smith handed her side a two-goal cushion prior to halftime when she added another penalty corner goal.
Australia's Kathryn Slattery scored to cut the lead to just one but Gemma Flynn and Olivia Merry struck for New Zealand in the third period to put the result beyond doubt as Slattery netted a late consolation.
Goals from Georgie Twigg, Helen Richardson-Walsh and Lily Owsley gave Britain a comfortable three-goal lead heading into halftime. Britain continued their dominance in the third quarter as they did not give Spain a sight of goal.
Spain piled on the pressure in the fourth period but left it too late as Georgina Oliva only managed to grab a consolation.
(Reporting by Shravanth Vijayakumar; Editing by Andrew Hay)
