Two-tour Lion Shane Williams grabbed two tries while Hook pulled the strings from fly-half and added 14-points with the boot.
Wales even survived a six minute spell down to 13 min after Bradley Davies and Leigh Byrne both found themselves in the sin-bin. But Scotland were unable to capitalise on the advantage and only managed to bag three points during that period.
Now Hook insists Wales are back in the race for the Six Nations crown with a trip to Rome next up.
"It was huge for us to get the win," said Hook. "We were really disappointed to lose to England on the opening weekend and if we had lost again it would've been really tough to come back from.
"But it was a good result and hopefully we can go on to beat Italy in two week's time. Then we come home to Cardiff and play Ireland.
"Potentially we could pick up three wins before facing France on the final weekend."
Wales flew into a 16-3 lead at halftime after surviving the tense spell down to 13 men and Hook has pinpointed that defensive effort as a crucial factor in the triumph.
"Our defence when we were down to 13 men won us the game," he added. "When you're attacking against 13 men you'd like to think you'd score but our defence was superb.
"It was tough but the boys worked hard and the last ditch defence was outstanding. We had them mentally after that and the effort from 1-22 was great."
Hook's break set-up Williams' first try and after impressing upon his return to the famous number 10 jersey the Ospreys play-maker is hoping he can hang on to his position.
"I enjoyed it and hopefully I can get another chance to stay there. There's always pressure on the Welsh No10 but it's important to concentrate on yourself and the team and not look to the outside influences."