Jonathan Tiernan-Locke is set to race his first senior road world titles with the support of defending champion Mark Cavendish as well as Tour de France winner Bradley Wiggins.
Cavendish has ruled himself out of contention for today's 267km race in Limburg but will start with the No.1 race number and do what he can for Great Britain.
The nation's approach to the world titles is different to that of last season where victory was the focus of a three-year plan. This year the event was somewhat an afterthought to the London Olympic Games road race and time trial - the latter in which Wiggins won gold and compatriot Chris Froome bronze.
Tiernan-Locke admits he is "unproven" at world championship level and is taking a step up in the Netherlands but is hopeful he can be at the finish of today's race, which he enters a week after winning overall honours at the Tour of Britain with the Continental Endura Racing team.
"I've had some good results and this is another level up again so I think the team's taken a bit of a leap of faith in me," Tiernan-Locke said.
"I'm happy to make the selection. I've done some easy rides, had a longer ride Thursday and I think that's important because Sunday is a longer race."
Great Britain has qualified a full quota nine-man team for the championship that includes Tiernan-Locke, Cavendish, Wiggins, Froome, Vuelta a Espana stage winner Steve Cummings, national champion Ian Stannard as well as Ben Swift, Alex Dowsett and Luke Rowe.
But the titles come toward the end of what has been a massive season for British cycling.
"Everyone is at different levels of fitness and mental states," said Wiggins who abandoned the recent Tour of Britain before the stage six start.
"I was in good shape at the Tour of Britain so managed to maintain some fitness and, like the rest of the guys, if I can play a role in some way towards the cause, whatever that is here, it's nice to be part of it."
Froome had been tipped as a potential team leader prior to competing at the Vuelta but too ruled himself out as another option on the course.
"I think it's going to come down to someone who is a little more explosive maybe," he said. "Personally I think it's going to suit somebody like (Philippe) Gilbert so that's not my typical style."
Froome has had little respite since the Tour in July where he finished second to Sky teammate Wiggins. The 27 year old carried on to the Olympics where he won bronze and then to the Vuelta in which he finished fourth overall.
"I'm definitely running out of steam but I'm keen to do a job on Sunday and try and hang on for as long as I can in the race," he said.
"Physically it's one thing, I think mentally it's also another thing just having to really stay on it and concentrating for that amount of time. When you're riding GC you need to be there each and everyday, being at the front, and thinking about what you're doing every second basically so that's I think what takes the biggest toll on you."
The peloton will cover 100km of undulating terrain from Maastricht before completing 10 laps of the finishing circuit, which incorporates the Cauberg, in Valkenburg today.
"It really does I think depend on what kind of race the guys ride," Froome said of potential outcomes.
"Spain want to ride a very aggressive race. They've got potentially eight guys who could try and go for a result. It's very open I think."
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