The Centre's decision to hold a cabinet meeting in Barcelona, instead of Madrid, sparked protests by pro-independence Catalans who blocked roads and major highways in the region on Friday.
Spanish Prime Minister Pedro Sanchez made the decision for a meeting to be held here on Friday as a push for decentralisation, almost a year after a failed independence movement in the region.
Scores of anti-riot police forces have been deployed outside the venue, while Al Jazeera reported that videos being circulated also showed protestors throwing bottles and flares at the law enforcement officials.
Sanchez had on Thursday issued a joint statement along with Catalonia's President Quim Torra pushing for an "effective" dialogue to settle the crisis in the region.
Catalonia is one of Spain's most prosperous regions that represents around 20 per cent of the country's economic output. Around 15 per cent of the nation's population or almost 7.5 million people reside in the region which includes the provinces of Barcelona, Girona, Lleida and Tarragona.