Zofino Muiuane was arrested after Mrs Guebuza was killed at their home in the capital, Maputo, police said.
Mrs Guebuza, 36, is the daughter of Mozambique's ex-President Armando Guebuza, who ruled from 2005 to 2015.
She married Mr Muiuane at a lavish ceremony, attended by regional leaders, in 2014.
While police said the shooting was a case of domestic violence, they also said they were still investigating the motive.
Mr Muiuane, a manager at Mozambique's first mobile phone company M-Cel, has not yet been charged.
Mrs Guebuza became one of Mozambique's wealthiest businesswomen during her father's presidency, our correspondent adds.
Business magazine Forbes listed her in 2013 as one of the 20 most powerful women in Africa.
BBC
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