The 18-hole tournament tees off on Monday morning at the Tomson Golf Club in Pudong, where Westwood, Poulter, US Open champion Rory McIlroy and Chinese number one Liang Wen-chong will compete over two holes.
The quartet will then split duties in the afternoon between a coaching clinic and a pro-am featuring a host of Asian celebrities including George Lam and Sally Yeh.
Westwood, who has had two stints as world number one in the past year, arrived at his hotel in Xintiandi following a 7½-hour flight from Manchester to Dubai and another 7½-hour flight from Dubai to Shanghai.
"It's one of those weeks where, a bit like going to Japan for the first time, you don't know what to expect. The schedule looks busy and it could turn into a bit of an adventure," said the 38-year-old, who is accompanied by caddy Billy Foster and manager Andrew ‘Chubby' Chandler, also McIlroy's manager.
"I've never done anything like this and the nearest I've heard about was the old Super Tour in Asia, which Chubby has told me about. I've been to Shanghai and Guangdong before, so I'm looking forward to seeing a bit more of China. There's a good bunch of us travelling around together."
Westwood has played in seven Ryder Cups and won 22 European Tour titles, and earlier this year won the Indonesia Masters and the Ballantine's Championship in South Korea.
Poulter, 35, was the first of the international players to arrive in Shanghai and felt energised despite a 15-hour flight from Newark, having begun his trip from Orlando.
"It was a long journey, but I feel fine. It's going to be a mad week, as I don't think any of us have ever done anything like this. It's going to be exciting," said Poulter, who beat world number one Luke Donald to win this year's Volvo World Match Play Championship.
"I had a look at the map of China to dot-to-dot the cities we're visiting and it looks like we're going to cover some miles. I've been to Shanghai, but I've never been to Beijing, Dalian, Macau or any of the other cities, so they're all going to be new to me."
Like Westwood, Poulter has enjoyed success on previous visits to Asia, having won the Barclays Singapore Open in 2009 and the UBS Hong Kong Open last year.
At Tomson, the players will compete over the 461-yard, par-four 16th and then the 590-yard, par-five ninth, which has water around the front, right and back of the green and features the picturesque clubhouse in the background.
McIlroy and Liang both competed at the venue when it hosted the former BMW Asian Open, a co-sanctioned European and Asian Tour event.
After the golfing activities, the players will return to the city centre and have a private dinner before Shui On Land chairman Vincent Lo accompanies the players on an evening tour of the famous Xintiandi shopping and entertainment district.
"The weather is spectacular so we hope it will be the same on Monday," said Lo, whose company is based in Shanghai and is famous for creating Xintiandi and other Tiandi developments in Chongqing and Dalian.
"Everything looks great at the club, so I'm looking forward to the first day. I've played with Lee twice before, but I'll be involved with Rory McIlroy and Liang Wen-chong in the coaching clinic, which should be a lot of fun."
McIlroy and his caddy John-Paul Fitzgerald were set to arrive on Sunday evening from Seoul, where the 22-year-old shot a closing 64 to finish runner-up in the Korea Open.
Liang is the lowest-ranked of the quartet, but the Chinese number one will enjoy massive support and greater knowledge of the courses.
The 33-year-old has won titles on the European and Asian Tours, and triumphed twice on last year's OneAsia circuit before finishing eighth in the PGA Championship, his best finish in a Major, after setting a new course record of 64 at Whistling Straits.
The quartet will be filmed throughout the jet-setting event. On Tuesday morning, the players will fly on Bombardier jets to Zhengzhou, capital of Henan province, where they will play the tournament's third and fourth holes at Jinsha Lake Golf Club.
The players then travel to Beijing - where they will compete at two golf clubs on Wednesday - before stops in Dalian, Chongqing, Dongguan and Macau.
Golf's most innovative competition, the Shui On Land China Golf Challenge is being broadcast globally on Golfing World and distributed internationally by IMG Media, while Sina, the largest Chinese-language infotainment web portal, is an official media partner.