The dates were decided by a draw held by the Spanish football federation Tuesday, which set the fixtures for the 38 match days of the 2013–14 season, which will run from August 17th this year to May 18th, 2014.
Real Madrid, under new coach Carlo Ancelotti, will head to the Camp Nou to face Barcelona on the weekend of October 27, with the return match in the Santiago Bernabeu on the weekend of March 23rd.
The exact date of La Liga fixtures is often decided nearer the time to avoid television scheduling conflicts.
Ancelotti will be hoping to improve on his predecessor Jose Mourinho's performance last season when Real surrendered their league title to Barcelona by 15 points and won no silverware other than the Spanish Super Cup.
Barcelona have strengthened their squad with Brazilian superstar Neymar for a reported €57 million ($73 million).
The 21-year-old led Brazil to victory over Spain in the Confederations Cup this summer.
He joins two-time La Liga record goalscorer Lionel Messi, at the Catalan club, replacing Spanish striker David Villa who was sold to Atlético Madrid for just €5.1 million.
Villa will face his former teammates when Spanish Cup winners Atlético go head to head with Barcelona in the first leg of the Spanish Supercup, scheduled for August 21st.