Spain's conservative Prime Minister Mariano Rajoy's conservative government has vowed to defend the unity of the country, as it recovers from a steep economic downturn, and has mounted a series of constitutional appeals to try to block the vote.
But Catalans have pushed ahead defiantly, fired up by the independence referendum held in Scotland in September, even though Scots voted not to break away from Britain.
Rajoy says his country cannot hold an independence referendum like Scotland because, unlike Britain, it has a written constitution that forbids it.
"What will take place tomorrow, we can call it whatever one wants, but it is not a referendum, not a consultation, nor anything that resembles it, I can't even qualify it. What is certain is that it will not have any effect," he said.
Proud of its distinct language and culture, Catalonia, a region of 7.5 million people, accounts for nearly a fifth of Spain's economy.
Demands for greater autonomy there have been rumbling for years, but the latest bid by the region's president Artur Mas has pushed the issue further than ever before.
But in 2010 Spain's Constitutional Court overruled that nationhood claim, fuelling pro-independence passions.
Spain's recent economic crisis has increased unemployment and hardship in the region and swelled its debts, but in 2012 Rajoy rejected Mas's request for greater powers for Catalonia to tax and spend.
In response, Mas vowed to hold an official yet non-binding vote on independence, but the Spanish government's legal challenges forced him to water that down.
Sunday's polls will be staffed by volunteers. Some 41,000 have signed up for the job.
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