Hundreds of people have been injured, some seriously, during the police crackdown on Catalonia's banned independence referendum.

Jordi Turull said 337 people had been hurt after police fired rubber bullets near at least one Barcelona polling station, and clashed with protesters throughout the region.

He blamed the violence directly on Spanish Prime Minister Mariano Rajoy and Interior Minister Juan Ignacio Zoido.

He said that actions by Spanish National Police and Civil Guard forces on Sunday were politically motivated and showed "a clear motivation to harm citizens".

Catalan international affairs director Raul Romeva said that regional authorities would appeal to European authorities over Mr Rajoy's government's alleged violations of human rights.

The people being hit by police did not come out to protest or riot, they are trying to enter a polling location. pic.twitter.com/t0Qd4orAxq

— Tim Pool (@Timcast) 1 October 2017

The officers fired rubber bullets while trying to clear protesters who were trying to prevent National Police cars from leaving after police confiscated ballot boxes from the voting centre.

Several people were injured during the scuffles outside Barcelona's Rius i Taule school, where some voters had cast ballots before police arrived. Catalan officials said 38 people were treated for mostly minor injuries.

(Emilio Morenatti/AP)

Civil guards clear people away from the entrance of a sports center, assigned to be a polling station by the Catalan government and where Catalan President Carles Puigdemont is expected to vote(Francisco Seco/AP)

Television footage showed police using batons to disperse the crowds gathered outside the local sports centre.

Catalan president Carles Puigdemont had been scheduled to vote there this morning. He has spearheaded the separatist politicians’ push to go ahead with the vote, despite a Constitutional Court suspension and fierce opposition by central authorities.

Spanish national police scuffle with people trying to reach a voting site(Emilio Morenatti/AP)

At least one woman was injured outside the building and wheeled away on a stretcher by paramedics.

Pro-referendum supporters clash with Spanish National Police(Emilio Morenatti/AP)

Polling station workers inside the building reacted peacefully and broke out into songs and chants challenging the officers’ presence.

National Police and Civil Guard officers also showed up in other polling centres where Catalan officials were expected.

Catalans defied rain and police orders to visit designated polling stations for the banned referendum on the region’s secession that has challenged Spain’s political and institutional order.

People link arms, after policemen where seen nearby, outside a school assigned to be a polling station by the Catalan government at the Gracia neighborhood in Barcelona(Bob Edme/AP)

Reporters saw ballot boxes wrapped in plastic bags being carried into some of the polling stations in Barcelona occupied by parents, children and activists before some polling stations opened.

The plastic ballot boxes, bearing the seal of the Catalan regional government, were placed on tables, prompting the cheering of hopeful voters that had gathered in schools before dawn.

A ballot box is carried into a voting site in a plastic bag(Felipe Dana/AP)

Some 2,300 facilities had been designated as polling stations, but it was unclear how many were able to open. The Ministry of Interior did not provide a number late on Saturday when it said that “most” of them had been sealed off and that only “some” remained occupied.

Police have received orders to avoid the use of force and only have been warning people to vacate the facilities. They are also supposed to confiscate ballots and ballot boxes.

In an effort to overcome myriad obstacles, Catalan officials announced that voters would be allowed to cast ballots in any location and using ballots printed at home, rather than in designated polling stations as previously announced.

Ballot papers and pens(Francisco Seco/AP)

Regional government spokesman Jordi Turull also said that a group of “academics and professionals” would serve as election observers. The official electoral board appointed by the regional parliament was disbanded last week to avoid hefty fines by Spain’s Constitutional Court.

“We are under conditions to be able to celebrate a self-determination referendum with guarantees,” Mr Turull said in a press conference. “Our goal is that all Catalans can vote.”