As a result, the Blue Devils' 42-game winning streak in ACC games at Cameron Indoor Stadium is over, and so is Elizabeth Williams' ACC-record string of 91 straight games with at least one blocked shot.
ACC newcomer Notre Dame became the first league team to win there since Maryland nearly six years ago.
"You've got to think about your defense more than you think about your offense," McCallie said. "If you score 16 but the other person scores 30, it's not exactly a productive day. So we've got to learn to value defense more."
Tricia Liston scored 23 points and single-handedly prevented Duke (21-2, 8-1) from being blown out by halftime.
"From our standpoint, we didn't shoot the ball well," McCallie said. "We didn't really move the ball. Everybody tried to do a little too much on their own, and that's not a good recipe for executing and having a little bit better offense."
Kayla McBride had 23 points and 11 rebounds, Jewell Loyd scored 17 points and Lindsay Allen and Natalie Achonwa had 15 apiece.
"We're going to have some tough games like that going down the road," McBride said. "We're in a new conference, new environments. I just think it's a good challenge for us."
This one wasn't much of a challenge at all.
Notre Dame (21-0, 8-0) made it look easy in its first visit to Cameron as an ACC member: The Irish never trailed, and held Duke to a season-worst 39 percent shooting and claimed sole possession of first place.
"It's a good win for us in February," coach Muffet McGraw said. "We've got a tough stretch in front of us, and we're not the type of team that likes to rest. We're ready for Florida State (Thursday night's opponent) by the time we get off the plane."
The Blue Devils threatened to get back in the game early in the second half, pulling to 49-44 on Richa Jackson's putback with 15 1/2 minutes left.
That's when Notre Dame got hot, scoring on six straight trips downcourt.
With Loyd hitting twice from close range and Michaela Mabrey making two outside jumpers, the Irish reeled off nine straight points during a 13-2 run.
Achonwa's free throw with 12:18 left gave Notre Dame its largest lead to that point, 62-46.
In winning this rematch of a 2013 NCAA tournament regional final, the Irish extended their school-record road winning streak to 31 and joined No. 1 Connecticut as the only teams to beat the Blue Devils at Cameron since 2008. They moved two wins from the best start in program history.
"You have three seniors who have been to Final Fours, back to back to back, and they have great leadership," Loyd said. "And then you go to the bench and you have a Hall of Fame coach. ... It helps a lot when you have that combo."
Jackson and Alexis Jones added 16 points each for Duke, which fell to 46-3 in home conference games under McCallie and have lost 11 straight games to teams ranked either No. 1 or No. 2.
Williams, plagued all day by foul trouble, finished with two points on 0-for-4 shooting.
"I'm sure I'll see a combination of passes missed into her and, at times, her being taken out by (Achonwa) when it comes down to watching film," McCallie said.
This marquee matchup in the new-look ACC matched the nation's top two shooting teams and the highest-scoring teams in the conference. Notre Dame entered shooting 51.4 percent and averaging 87.3 points while Duke shoots 51.1 percent and scores 84.4 points per game.
The Irish continued to shoot that well in this one.
The Blue Devils didn't.
McBride, who had 14 points at halftime, was called "the best guard in the country" by McGraw.
She helped Notre Dame lead by 14 in the first half after forcing Duke to miss 19 of its first 29 shots and reeling off 11 straight points to push its lead into double figures for the first time.
Allen capped that burst with a layup that made it 37-23 with just under 5 minutes before the break.
Liston hit six shots in the half -- or, one fewer than the rest of her teammates combined.