Asisat Oshoala was on target but Barcelona were silenced 4-3 by Atletico Madrid in Tuesday's Primera Division Women's outing.
Prior to this game, the Blaugranes had celebrated a treble after defeating Levante 4-2 in Sunday's Copa de la Reina final.
That victory also saw them extend their winning streak to 28 games across all competitions in the 2020-21 campaign.
Against the Mattressers, however, their invincible run was ended in the seven-goal thriller.
Having bowed 1-0 at home to Levante last time out, Dani Gonzalez's women began the game on a bright note.
That paid off as Amanda Sampedro gave them the lead after 12 minutes after profiting from a Deyna Castellanos assist.
The lead lasted for just seven minutes as the visiting side leveled matters courtesy of Bruna Vilamala's strike after she was teed up by defender Jana Fernandez.
Nine minutes before the half-time break, Oshoala put Lluis Cortes' team ahead with a delightful finish thanks to fine work from captain Vicky Losada.
That effort saw her end her seven-goal drought. In addition, it was her 16th goal in 22 Spanish elite division outings.
Like a house on fire, the hosts came back stronger in the second half, and two quick goals meant they were back ahead.
First, French forward Emelyne Laurent converted Kylie Strom's cross in the 58th minute before Laurent added a second eight minutes later. This time, it was Venezuelan star Castellano who supplied the assist.
Marta pounced on a rebound to set up Alexia for a Barcelona equaliser in the 74th minute.
However, it was Castellanos who had the final say for Atletico Madrid in the 80th minute.
While reigning African Women's Player of the Year Oshoala was in action from start to finish, her compatriot Rasheedat Ajibade was in action for 46 minutes for the hosts.
Elsewhere, Cameroonian forward Ajara Nchout was introduced for Brazil's Ludmila in the 89th minute.
Barcelona were already crowned champions of the Spanish women's topflight.
Oshoala and her teammates would be hoping to return to winning ways when they host Madrid in their next outing on Sunday morning.