The Lions take on the Cheetahs in the third game of their 10-match tour of South Africa on Saturday afternoon and Hook admits he is delighted to be involved.
The 23-year-old missed out on original selection for Ian McGeechan's elite touring party but won a dramatic call up on the eve of the Lions' departure for the Republic following injury concerns surrounding fellow Welsh international Leigh Halfpenny.
"It is a huge honour to wear the Lions jersey and a great responsibility as a Welshman to play at No 10," said Hook, who contributed 11 points as a second-half replacement in Wednesday night's win over the Golden Lions in Johannesburg.
"When they announced the team, they gave us a list of some of the great players who have worn the jersey before. In my case it was players like Barry John and Phil Bennett."
Having been selected at No10 for the tourists in Bloemfontein, Hook has made it clear that outside-half is his undoubted position of choice.
Although he has played centre and full back for both region and country and has stated he would play anywhere for the Lions, Hook knows that Saturday's clash with the Super 14 side from the Orange Free State represents his biggest chance to press his claims for a Test place against the Springboks on June 20.
"I do prefer to play at outside-half, but when Ian McGeechan called me up into the Lions party he said I'd have to play in a number of positions.
"I'd play anywhere for the Lions, but this is my big opportunity.
"There is no point in coming out her and sitting back. I want to show them what I can do."
The Lions arrive in Bloemfontein on the back of successive, yet contrasting, wins in their opening two fixtures.
A nervy start against a Royal XV in Phokeng was followed by a stunning 10-try triumph over the Golden Lions four days ago, with the manner of the latter of those performances boosting confidence inside and outside of the Lions camp.
With just a fortnight to go until the first Test against the world champions in Durban, the Lions know that momentum must continue to be built if they are to increase their chances of success against the mighty Springboks.
Despite the comprehensive nature of Wednesday's win, Hook and his colleagues are under no illusions as to the size of the challenge posed by the Cheetahs.
McGeechan has named a side including 11 Magners League players but showing a full 15 changes from their last outing at Coca Cola Park.
Youngsters Luke Fitzgerald and Leigh Halfpenny have left their mark on the Magners League this season and are both set for their Lions debuts, while Hook, Ellis, Northampton prop Euan Murray, Edinburgh hooker Ross Ford, Munster lock Donncha O'Callaghan, Ulster flanker Stephen Ferris and Cardiff Blues No8 Andy Powell will all make their first starts in Lions colours.
"Any game in Bloemfontein is going to be a hard one," said Lions head coach McGeechan.
"The Cheetahs finished strongly in the Super 14 and did very well in beating the Sharks and the Crusaders.
"They also pushed the Bulls hard and there are some very good players in their side. They are minus a few, but they still have a few Springboks in their ranks.
"We are settled now and the players are all keen to put on the Lions jersey and get a start. The more they train together the better their understanding of each other and how we want to play.
"We have to keep things in perspective - there are things we have to become better at. Wednesday has given us some excitement about what we are doing and it has given us some belief. But that is going to be challenged this weekend and through the rest of the tour."
British & Irish Lions: Lee Byrne (Ospreys / Wales); Leigh Halfpenny (Cardiff Blues / Wales), Keith Earls (Munster / Ireland), Luke Fitzgerald (Leinster / Ireland), Shane Williams (Ospreys / Wales); James Hook (Ospreys / Wales), Harry Ellis (Leicester Tigers / England); Andrew Sheridan (Sale Sharks / England), Ross Ford (Edinburgh / Scotland), Euan Murray (Northampton Saints / Scotland), Donncha O'Callaghan (Munster / Ireland), Paul O'Connell (Munster / Ireland - Captain), Stephen Ferris (Ulster / Ireland), Joe Worsley (London Wasps / England), Andy Powell (Cardiff Blues / Wales)
Replacements: Matthew Rees (Scarlets / Wales), Adam Jones (Ospreys / Wales), Simon Shaw (London Wasps / England), Nathan Hines (Perpignan / Scotland), Gordon D'Arcy (Leinster / Ireland), Ronan O'Gara (Munster / Ireland), Mike Blair (Edinburgh / Scotland)
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