The home side opened the scoring in the fourth minute when Emerging Springbok fly half Willem De Waal banged over a straight forward penalty in testing conditions. His effort was quickly cancelled out by Stephen Jones and the Welsh stand off.
The Lions hit the lead for the first time in the 11th minute after Western Province loosehead prop Wicus Blaauw failed to counter Phil Vickery in the scrum. Jones required the woodwork but his second penalty put the Lions 3-6 in front.
The Lions continued to ask questions of the Western Province defence with full-back Joe Pietersen having a particular torrid time. However the home side weathered the storm and equalised through a well struck De Waal drop goal in the 19th minute.
The Lions had the wind at the backs but were struggling to take advantage of the conditions. De Waal was using his left foot to great effect to get Western Province in to the right positions. Pietersen snapped over a drop goal to put the Province 9-6 ahead in a game of fluctuating fortunes.
The Welsh connection of Andy Powell and Martyn Williams set the Lions backs away with Tommy Bowe brushing of three defenders to score out wide. Bowe turned try scorer to try provider when he sliced through the Province defence to set up his fellow wing Ugo Monye who dived in at the opposite corner. Jones's sideline conversion put the Lions 9-18 in front.
The Lions pulled down a ruck right on the hooter to give De Waal a chance to close the gap - he never looked like missing as the players went down the tunnel with the Lions leading 12-18.
Having used a long range effort as a sighter, De Waal punished the Lions further when Joe Worsley and Williams were caught off-side to bring the home side within three points of the Lions after 48 minutes.
Williams used all his experience to wield away from a ruck to score wide out in the 55th minute but De Waal ensured is side stayed in touch with another penalty.
Province then burst into life with lock Anton Van Zyl surging into the Lions 22. Quick ball then saw De Waal off-load a perfect pass to Pietersen who was standing out wide and who had too much gas for Euan Murray out wide to levels matters at 23-23.
Hook then delivered a hammer blow to Western Province's hopes of becoming the first side to lower the colours of the Lions. With four minutes remaining he landed a crucial penalty to send the tourists 23-26 ahead.
Lions: Rob Kearney (James Hook 64); Tommy Bowe, Keith Earls, Riki Flutey, Ugo Monye; Stephen Jones, Harry Ellis; Andrew Sheridan, Matthew Rees (Ross Ford 56), Phil Vickery (Euan Murray 56), Donncha O'Callaghan, Nathan Hines (Simon Shaw 56), Joe Worsley (Tom Croft 70), Martyn Williams, Andy Powell.
Replacements: (Not used): Shane Williams, Gordon D'Arcy.
Scorers: Western Province: Try - Pietersen; Pens - De Waal (4); Dgls - De Waal, Pietersen.
Lions: tries - Bowe, Monye, Williams; Con - Jones; Pens - Jones (2), Hook