The 134-mile coast-to-coast pathway takes in some of the country's most striking scenery and landscapes, as well as wildlife sites and historic visitor attractions.
First Minister Alex Salmond said: "John Muir was a remarkable Scot – a man whose passion for nature and the outdoors left an incredible environmental legacy that resonates to this day.
"From humble beginnings in Dunbar, his influence spread across the world and his name now adorns parks, glaciers and mountains. His legacy is celebrated in an annual commemorative day in California and his image has featured on two US postage stamps.
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"There is no more fitting tribute, in 2014 the 100th anniversary of his death and in our Year of Homecoming, than to officially open the John Muir Way from Helensburgh to Dunbar and take walkers and cyclists through 134 miles of splendid scenery in Scotland's heartland.
"The route will encourage many thousands of people to get out into the outdoors, get some exercise and enjoy the iconic scenery of Muir's country of birth."
The Minister continued: "As well as the health benefits, the new John Muir Way is expected to help Scotland's tourist industry and around £40 million in economic benefits are expected to be brought to the many communities that are connected along the route.
"I am sure the new John Muir Way will be an incredible success and I hope that the many, many thousands of people who will make their way along it in the coming years enjoy a magnificent day out."
Ian Ross, Chairman of Scottish Natural Heritage (SNH), added: "This route has been a long time in the planning and is now a very important resource for people of any ability or fitness living or visiting Scotland.
"You can walk a mile along the route near where you live or walk the entire 134 miles. The route is an easy and enjoyable way for the 3 million people who live in the Central Belt to enjoy the outdoors every day by foot, bicycle, and even by horseback in some places."
(JP/MH)
