Analysts say his death is likely to intensify turmoil in President Robert Mugabe's party over the question of who will succeed the 87-year-old leader.
Under his nom de guerre, Rex Nhongo, he was the director of Mr Mugabe's forces during the 1970s' war of independence.
An official source told the BBC Gen Mujuru died in a fire at his farmhouse in Beatrice, about 80km (50 miles) south of the capital, Harare, in the early hours of Tuesday.
It is unclear if he was alone at the time or if he was provided with security by the army.
President Mugabe is expected to deliver the official statement confirming the death of Gen Mujuru later in the day - in accordance with Zanu-PF party protocol.
The BBC's Brian Hungwe in Harare says Gen Mujuru was a senior politburo member in the Zanu-PF party and regarded as a moderate.
He was a strategist and rumoured kingmaker in divisive Zanu-PF succession politics, he says.
His death will create a void and leave his wife - one of the country's two vice-presidents - exposed, analysts say.
During the war against Rhodesian rule in the 1970s, Gen Mujuru led the armed struggle together with the late Josiah Tongogora.
Our reporter says it was Gen Mujuru who implored the freedom fighters in Mozambique during the conflict to accept Mr Mugabe as the leader of the Zanla rebel movement forces after his release from detention in 1974.
At independence in 1980 he took over the command of the army, before retiring and going into business 10 years later.
Our reporter says as the leading commander of the liberation war against colonial rule, he is expected to be buried at the national shrine, Heroes Acre, some time this week.
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