The country's unemployment rate rose to 24.6% during the April to June quarter, up from 24.4% during the previous quarter.
That is the highest rate since the mid-1970s, when the right-wing dictator Francisco Franco died and the country reintroduced democracy.
Separately, Spain's third largest bank reported an 80% fall in net profits.
CaixaBank said net profits fell to 166m euros ($203m; £129m) during the January to June period. On Thursday, Spain's biggest bank, Santander, reported that its profits halved during the period.
CaixaBank also set aside 2.7bn euros against its property assets, in accordance with reform requirements stipulated by the government in May.
Spain's economy is in dire straits and economists see no signs of improvement any time soon.
"Things are only going to get worse," said Capital Economics' Ben May.
BBC News - Spain unemployment hits new high