The president has also approved sending 20 armored Humvees and up to 200 unarmored Humvees under a separate authority.
The announcement comes as President Barack Obama continues to weigh sending lethal aid to Kiev, a move he's so far resisted amid pressure from Democrats and Republicans alike. Last month he said at a press conference alongside German Chancellor Angela Merkel that diplomatic efforts to end the violence needed time to take hold.
An administration official said on Wednesday that the White House "continue(s) to believe that there is no military resolution to this crisis" but that "Ukraine has the right to defend itself."
Vice President Biden informed Ukrainian President Petro Poroshenko of the new assistance in a phone call, the White House announced.
The Vice President "noted with concern the ongoing violations of the ceasefire by Russia-backed separatists near Donetsk and Mariupol and their refusal to allow OSCE monitors unfettered access to the territory they occupy," according to the White House statement.