The Samoan side had looked to dominate the collision area but it was Wales who had the upperhand in the physicality stakes with Jamie Roberts and George North making telling runs which resulted in Seilala Mapusua and Tasesa Lavea coming off second-best.
Paul Williams tied the scores on the 20th minute with a penalty of his own after Wales were penalised for not keeping their feet at the ruck.
Hook added his second penalty in the 25th minute after a wealth of possession in the Samoan half. The Welsh Dragons settling for three points when it looked as though they were a phase or two away from scoring the first try.
However that reward would fall to Samoa who eventually got the breakthrough after a wave of attacks on the Wales tryline.
In the 41st minute prop Anthony Perenise ducked a tackle and muscled over for the first try.
If the firsthalf was built on brutal defence and hard-running, the secondhalf ran solely on the sheer determination of the men on the field.
Rys Priestland kicked two penalties to push his side in-front 12-10 and with 15 minutes remaining Wales would strike the killer-blow.
Leigh Halfpenney escaped the tackles of Seilala Mapusua and George Pisi before scooting 60 metres upfield, he threw a pass back infield which bounced for Shane Williams to pick up and score.
Welsh fans went wild and the large Samoan contingent were stunned that a try of that length had been let through after both teams gave little attacking metres throughout the match.
The final 15 minutes was a tense affair as Samoa tried to penetrate the Welsh line yet they were met by a water-tight defence.
Wales held firm for a famous victory and more importantly the continuation of their Rugby World Cup campaign.
Wales 17 (Shane Williams try; James Hook 2 penalties, Rhys Priestland 2 penalties) def. Samoa 10 (Anthony Perenise try; Paul Williams conversion, penalty). HT: 6-10.
- HERALD ONLINE