La Liga's decision to broadcast the first El Clasico of the season at 3:15 UK time means that fans in Britain will be unable to watch the game live on television.
Barcelona and Real Madrid will meet for the first time in the league at the Nou Camp on December 3, but a long-standing British broadcasting rule means the game will not be shown live on British television.
FA rules prohibit any football being shown on television between 2:45pm and 5:15pm.
As in previous years, the game will be shown, in full, on a delay from 5:15pm on Sky Sports.
La Liga president Javier Tebas defended the time-slot insisting the decision was made to maximise the match's worldwide audience.
"The Barcelona and Real Madrid game will be played on Saturday at 4:15 p.m. The game will not be aired in England because of the TV embargo that is placed at that time," Tebas told Spanish radio station, Cadena Ser.
The kick-off time means the game will be available to watch in over 100 countries, including the growing audience in America.
"We had three windows we had considered, at 1pm, 4:15 pm and 6:30pm. We analysed those with our audiovisual team and to play at 6 pm is too late in Asia while to play at 1pm is too early for the American market."
"I look at other leagues when setting the timetable," Tebas said.
"The timetable is a strategy we have been working on in recent years and the results are there. Our international sales have tripled because of that and the quality of the players we have in our league.
"We are continuously looking at ways that we can improve our product. For example, we have installed aerial cameras in seven venues and by the end of the season, we will have that in three more stadiums.
Defending champions Barcelona are currently fourth in La Liga, two points adrift from rivals Real Madrid who are level on points at the top of the table with Atletico Madrid.