The couple's children, aged four months to nine years old, were lightly injured in the shooting yesterday and taken to hospital, an Israeli security source said.
The victims were named as Eitam and Naama Henkin, both in their 30s and residents of the central West Bank settlement of Neria, near Ramallah.
They "were massacred right in front of their four children," Israeli army spokesman Peter Lerner said in a statement.
The incident took place between the Jewish settlements of Itamar and Elon Moreh, near the Palestinian city of Nablus.
Also Read
Israeli Defence Minister Moshe Yaalon said in a statement that the security forces "will spare no efforts to arrest the killers and their sponsors."
Israeli security forces flooded the sector where the incident occurred, an AFP journalist saw.
The international community regards all Jewish settlements in the West Bank as illegal, but the Israeli government makes a distinction between those it has authorised and those it has not.
The shooting also came after Israeli Prime Minister Benjamin Netanyahu offered in a speech at the UN General Assembly to resume direct peace talks with the Palestinians.
The premier said he was prepared to "immediately resume direct peace negotiations" without preconditions, although the Palestinians condition a resumption of dialogue on an end to settlement building and the release of prisoners.
"The time for talking (with the Palestinians ) is over," Israeli Education Minister Naftali Bennett thundered in a statement following yesterday's attack.
"It is time to act," he added, saying that "people whose leaders support the murder will never be a state.