The turning point in his career came in 1683 when Melville and his son David Leslie-Melville, the Earl of Leven, were accused of complicity in the Rye House Plot - a Whig conspiracy to assassinate King Charles II and his brother the Duke of York (the future James VII).
To escape arrest Melville, together with his son, Leven fled to the Netherlands where they joined the band of British Protestant exiles at the court of Prince William of Orange.