Charles, known as the Duke of Rothesay in Scotland, toured the eight-floor tourist attraction set in one of the capital’s landmark heritage buildings and met employees.
He unveiled a plaque on the rooftop terrace bar which has views of Edinburgh Castle.
Located in the former House of Fraser building, the centre is part of a £185 million investment in the drinks company Diageo’s venues and distilleries around Scotland.
During his visit, Charles met the first students in the Johnnie Walker Learning For Life Academy; it is a new space dedicated to the bartender and hospitality training programme.
They were joined by representatives of The Prince’s Foundation’s introduction to hospitality courses that run at the charity’s headquarters, Dumfries House in Ayrshire.
This marked the launch of a partnership between Johnnie Walker and The Prince’s Foundation to deliver training and employment opportunities to support the sustainable recovery of hospitality and tourism across Scotland.
In celebration of the partnership, the students prepared a bespoke Duke of Rothesay cocktail for the royal visitor, created with Johnnie Walker Autumn, the first seasonal whisky exclusive to Johnnie Walker Princes Street, and garnished with ingredients from the gardens at Dumfries House estate.
Before signing the Johnnie Walker ledger book to mark the end of his visit, he enjoyed a sip of his drink on the rocks and joked: “These are the biggest blocks of ice I’ve ever seen.”
Laid out across 71,500 square feet, the centre will host host tours, tasting experiences and live performances.
Diageo chief executive Ivan Menezes hosted the Charles on the tour, along with Diageo president for supply chain and procurement Ewan Andrew, and Johnnie Walker Princes Street managing director Barbara Smith.
Mr Menezes said: “It has been an honour to welcome His Royal Highness The Duke of Rothesay to officially open Johnnie Walker Princes Street and a pleasure to celebrate this special moment with our people and the students we are training for an exciting future in the hospitality industry.
“We are grateful to His Royal Highness for the interest he has shown in the Scotch whisky industry and we look forward to working in partnership with The Prince’s Foundation to create opportunities for people in communities across Scotland to get into training and employment in hospitality and tourism.”
Earlier on Friday, Charles joined the Queen at Balmoral Castle in Aberdeenshire to plant a tree to mark the start of planting season for the Queen’s Green Canopy (QGC) initiative, created to highlight her 70 years’ service to the nation, which urges people to “plant a tree for the jubilee”.
He then travelled to Edinburgh where he joined Camilla, known as the Duchess of Rothesay in Scotland, at the Royal Botanic Garden Edinburgh of which he is a patron, to mark its 350th anniversary year in person a year on, after the coronavirus pandemic forced changes to the celebrations.
Camilla went on to mark the 25th anniversary of the opening of the first Maggie’s cancer support centre, a charity of which she is president, which opened in the city in 1996.
Charles attended various other engagements in the city before appearing at the Kirking of the Parliament at Edinburgh’s St Giles Cathedral.
The kirking is an ecumenical service of blessing on the eve of the opening ceremony to the sixth session of the Scottish Parliament.