The body will represent companies with £17 billion of turnover and 150,000 employees.
Chris van der Kuyl, chairman of Entrepreneurial Exchange said: "By combining our strengths we build strategic linkage between the talent Saltire enables and the expertise our businesses need."
Peter Lederer, chairman of Saltire added: "As a small nation Scotland needs to drive maximum efficiency from its resources to maximise economic return. Creating Entrepreneurial Scotland does just that.
"Equally, to be clear, this new entity will seek to enable further partnership across the entrepreneurial sector to deliver on that principle."
ES, which will be formally launched next month will be a non-profit organisation with the Saltire Foundation as a charitable subsidiary.
Saltire Foundation chief executive Sandy Kennedy is to be chief executive of the new body which Mr van der Kuyl will chair. Entrepreneurial Exchange members will become fellows of ES.
Ayrshire entrepreneur Sir Tom Hunter said: "This move will enable an accelerated drive to build Scotland's entrepreneurial community in a strategic, well thought out move that is for entrepreneurs, by entrepreneurs, an ethos that serves Scotland well."