They are accused of opening fire on dozens as rebel forces closed in on the capital during the uprising against former leader Colonel Muammar Gaddafi.
It is thought to be the highest number of death sentences handed out since the overthrow of the regime, AFP reports.
Libya has struggled to restore peace since the uprising seven years ago.
Aside from the 45 sentenced to death, 54 more were given five-year jail terms and another 22 were acquitted of charges relating to demonstrator deaths.
It was not known when the accused were arrested, charged or prosecuted.
The case, referred to by the Libyan Justice Ministry as Abu Salim No 2015-1477, is known locally as the Triq al-Sareeh case.
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