The general election caps off a year of electoral change in southern Europe after far-left party Syriza was swept to power in Greece in January and a coalition of leftist parties in Portugal pooled their votes in parliament to unseat the conservative government after an inconclusive election in October.
Spain has been dominated for more than three decades by the conservative Popular Party and the main opposition Socialists, who have alternated running the government.
Ciudadanos leader Albert Rivera said Spain "was on the threshold (of) a new era" after he cast his ballot in L'Hospitalet de Llobregat in the northeast.
Polls predict Prime Minister Mariano Rajoy's Popular Party (PP) will win the largest share of the vote but not enough to retain its absolute majority in parliament.
Such a result would force it to form an uneasy alliance with another political grouping or attempt to rule as a minority government.
Rajoy appealed for a high turnout as he cast his ballot in Madrid.
"What we all want is that the greatest number of people take part in the vote. It is an important decision," he said.
The government said that at 6:00 pm (1700 GMT) turnout stood at 58.36 per cent percent, 0.71 percentage points higher than at the same time in the last such elections in 2011.
"The PP and the Socialists became complacent and they have forgotten about us. We have to give the new parties a chance," said grey-haired truck driver Francisco Perez, 53, after voting for Podemos in L'Hospitalet de Llobregat.
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