The menus had to include shellfish in the starter, venison in the main course and British apples within the dessert.
It means that Selby has won two prestigious cooking competitions in the same year, having taken the title of Roux Scholar in April.
He created a menu of sea vegetable minestrone, mussels and farfalle pasta served with a poached scallop, British caviar and a lemongrass scented buttermilk sauce; roasted fallow deer, blackberry, celeriac, sprouts and bacon served with a venison sauce finished with chocolate; warm walnut almondine, ginger-infused bramley purée, caramelised Cox apple filled with an apple compote, cinnamon and ginger ice-cream.
Speaking about winning National Chef of the Year, he said: "I'm speechless. I really wasn't expecting it. I'm chuffed. The competition was tough but I was happy with everything I did. I'm going to go home and sleep now! It's been a busy few days preparing for the competition. I've been practicing every day for the last two weeks since I submitted my menu."
Winners take home not only the title but a medal, a membership to the Craft Guild of Chefs, media training session worth £7,500 and a recipe book provided by Knorr, an all expenses paid trip to Mexico from Lockhart, a trip to Switzerland from Nespresso, where they will take part in a training programme, a framing plate and £500 worth of vouchers from Churchill, the chance to design their own chocolate from Cacao Barry, and meal for two at Pétrus followed by a one-week work placement.
The judging panel, which was chaired by Belmond Le Manoir aux Quat'Saisons executive head chef Gary Jones, included Sat Bains, Simon Hulstone, Philip Howard, Lee Westcott, Benoit Blin, Claude Bosi, Clare Smyth, Frederick Forster, Graham Hornigold and Tom Kerridge.
Jones said: "I think this is the strongest line-up we have ever seen. Some guys, super-strong cooks, didn't make it through the semis, so I was really excited to see how they would perform today. The marks were really tight on this. What the judges were looking for was simplicity, consistency, cooking skills and approach, and food which is a pleasure to eat. Everything that came up our way was fabulous, we were spoilt today."
Vice-president of the Craft Guild of Chefs and organiser of the competition David Mulcahy said: "This competition and this day has been phenomenal. We are faced with an uncertain future and when you look around at the talent you can see we are in a great place if we invest in these people today."
He added: "We had 10 very strong finalists but Luke was a very worthy winner. Luke understands how to perform under pressure. It doesn't mean you are going to win just because of that though. Luke has previously won the Young National Chef of the Year and this year he won the Roux Scholarship - he's on a roll. He has an edge which is unique and innovative, he doesn't play safe but he understands food and ingredients. He is a great winner and will be a great ambassador too."
Ten finalists, from over 100 entries, competed at the Restaurant Show at Olympia London during a live cook-off today.
Other finalists included: Ben Champkin, sous chef at L'Enclume, Cartmel, Cumbria; David Davey-Smith, chef at Royal Air Force Worthy Down; Will Holland, head chef at Coast restaurant, Saundersfoot; Karl O'Dell, senior sous chef at Petrus, London; Dean Westcar, head chef at Restaurant Hywel Jones, Lucknam Park, Colerne, Wiltshire; Thomas Westerland, sous chef at Lucknam Park; Kuba Witkowski, head chef at the Feathered Nest Inn, Nether Westcote, Oxfordshire.
Last year's National Chef of the Year was James Devine.
The competition is open to chefs who are 24 years or older on 1 February 2017 and working in any area of the hospitality business including hotels, restaurants, pubs, contract catering, fine dining, private and public sectors, and may be working in the UK or overseas.
Mulcahy also announced that an alumni of past winners will be taken on a gastronomic trip to Venice next year.
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