Some 16 students of the Upper Sixth Form, who usually travel from Wolverhampton to Newport by bus, decided to make their journey on foot.
The usual 50 minute trip took them more than eight hours to complete as they braved both the wind and rain to complete their journey.
But their efforts were rewarded when they arrived to discover that they had raised £3,600 via the Cancer Research UK donations page.
Sarah Reynolds, head of marketing at the school, said: "We have some 1,054 students enrolled and the sponsored walk was one of their charity activities during the week.
"Those taking part in the 20-mile trip ended up walking 23 miles because of some dodgy map-reading.
"They walked alongside the Shropshire Union Canal to Gnosall and turned left onto a disused railway to walk into Newport.
"The students set off at 2am and finally arrived shortly before 10.30am but one of those taking part slipped on the muddy tow-path and fortunately avoided completely falling into the canal.
"During the week of activities, organised by the Charities Committee which is made up of six students and four staff, students take part in various events.
"Everyday is dress-up day with themes such as Pyjama Day and Odd-Sock Day.
"Bake-Off involves food sold at break-times and lunchtime.
"Later in the week there will also be sponge-throwing at the teachers.
"There will also be various sports activities which will see students competing against staff members."
"The events raise funds for five charities which are both national and local."