Teachers, parents, students and activists in this wealthy northeastern region have leapt into action to defend the vote slated for tomorrow, defying Madrid's warnings of repercussions by occupying more than 160 schools designated as polling stations, it said.
Enric Millo, the central government representative in Catalonia, told reporters 1,300 polling stations had already been sealed off.
He said that 163 of those had already been occupied when they were sealed off, which meant those inside were allowed to leave but no one could go in.
The standoff between the central government and Catalan leaders over an independence referendum opposed by Madrid has morphed into one of the biggest crises to hit Spain since democracy was restored after the death of dictator Francisco Franco in 1975.
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As such, it has Spaniards the country over worried.
In Spain's major cities, Madrid, Barcelona, Sevilla, Santander, Alicante, Valencia and Malaga, thousands protested for Spanish unity.
Catalan separatist leaders and organisers of "committees to protect the referendum" stressed that everyone must remain peaceful.
In one incident, though, someone fired a pellet gun on last night at a group of people standing in front of an occupied high school in the Catalan town of Manlleu, lightly injuring three people, police said.
The referendum has sown divisions among Catalans themselves, with the region deeply split on independence, even if a large majority want to be allowed to settle the matter in a legal vote.
For days, they have been seizing electoral items such as ballot papers while prosecutors have ordered the closure of websites linked to the vote and the detention of key members of the team organising the referendum.
But those for the vote have mobilised.
Yesterday, tractors paraded through Barcelona, some decked with the "Estelada", the separatists' flag of red-and- yellow stripes with a white star on a blue chevron.
They and firefighters have pledged to protect polling stations.
From district to district, people gathered to form "Committees to protect the referendum", using the Telegram messaging app to get organised and urging everyone to remain peaceful, said an AFP correspondent who saw some of the messages.
Carles Riera, a lawmaker in the regional parliament for the radical CUP party, part of Catalonia's separatist coalition, vowed that mobilisation would continue after Sunday's vote -- if the "yes" camp won but Madrid opposed the result, as is almost certain.
"We're in a process of popular mobilisation that is going to last a while," he told reporters.
"This democratic wave, this level of auto-organisation will have to keep going for a long time to defend the republic."
Yesterday, Spain's education ministry said in a statement that head teachers in Catalonia "were not exempt from liability" if they cooperated and allowed their schools to remain open for the vote.
Barcelona's Joan Brossa high school, for instance, advertised a series of activities for yesterday and today, including film screenings, football matches and Zumba dance fitness classes.
It remained unclear though how people would be able to enter sealed-off schools tomorrow to vote, even if they are occupied.