Joe Fattorini visits South Africa where he finds out about whether Napoleon and Charles Dickens' favourite drink has withstood the test of time. Chef Brad McDonald tells us about his favourite grape and cooks a dish to complement it and we learn about whether a wine made by a tattooed punk in Australia can have anything in common with one made at Château Margaux, one of the world's most exclusive vineyards.

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In South Africa, Joe explores issues of environment and sustainability. Matthew Goode and Matthew Rhys visit Vatican City, learning about wine and the Catholic Church. Amelia and Joe face off over alpine wines and vin chaud in Megève.

In southern Chile, Joe observes winemaking in the face of adversity and natural disaster, before heading to the wine cellars of Cricova in Moldova. Matthew Goode and Matthew Rhys head to Tuscany, attempting to avoid a 'fiasco'.

Joe learns more about wine's place in history and Judaism in Jaffa, Israel. Matthew Goode and Matthew Rhys examine wine labels, art and identity at the Nittardi winery. In the Napa Valley, Gizzi has a rendezvous with some local wine makers.

In Shanghai, Joe truly immerses himself in an expanding wine culture, facing challenging new flavours, foods and perspectives on wine. Matthew Goode and Matthew Rhys return to Rome to find a sweet wine.

Joe takes part in a famous wine auction in Beaune, Burgundy. Matthew Goode and Matthew Rhys make their way to Bologna to find a match for pasta whilst learning about local cuisine. Amelia talks about family history in the Barossa Valley.

Amelia and Joe rediscover port, as well as table wines, in Portugal's Douro Valley. Matthew Goode and Matthew Rhys visit Verona, searching for romance in a bottle. Joe looks for fine wines in Chile.

Joe travels to Hong Kong, one of the world's biggest markets for fine wine. Matthew Goode and Matthew Rhys journey to Trentino to talk biodynamic winemaking and terroir. Amelia reminisces over fortified wines in the Barossa Valley.

Seeking to understand the many faces of South Africa's wine industry, Joe visits two very different wineries. Reversing roles, the Matthews send Joe to Orvieto to find a 'transgressive' wine. The trio then explore the issue of wine fraud.

In Santorini, Joe learns about Greek wine old and new. Matthew Goode and Matthew Rhys seek to complete The Wine Show case in Venice, sampling several aperitivos. Amelia discusses the challenges of climate change in Adelaide and Tasmania.