The new boss' first match in charge of the Baggies could not have gone better as they picked up a fairly surprising three points, with the Chelsea loanee impressing from the bench
Liverpool were the better of the two teams in the first half but fell behind late in the first period as Zoltan Gera fired a sensational half-volley into the top far corner.
The second half followed a similar pattern and although Pepe Reina saved a Shane Long penalty, he could not stop Peter Odemwingie's spot-kick or Romelu Lukaku's late header as Brendan Rodgers endured a miserable start to his tenure.
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Despite bringing in a number of players over the summer, only one new signing started for the Baggies as Claudio Yacob sat alongside Youssouf Mulumbu in midfield, while the likes of Yassine El-Ghanassy and Romelu Lukaku started on the bench.
Both of Liverpool's summer signings had places in Brendan Rodgers' starting XI, as Fabio Borini partnered Luis Suarez in attack, and Joe Allen sat deep with Lucas Leiva in midfield, while in defence Glen Johnson started at left-back due to the unavailability of Jose Enrique.
The match started in a lively fashion and fairly end-to-end, with Luis Suarez having a good opportunity on the break, then seconds later Shane Long was fouled on the edge of the Liverpool area after springing his own counterattack, but Steven Reid wasted the free kick.
The Uruguayan was involved again a few minutes later as he cut inside and into the penalty area from the left-hand side, but just as Steven Gerrard was able to fire the forward’s cut-back goalwards, West Brom debutant Yacob was in the right place to make the block.
Suarez was certainly looking the most likely player to create something for Liverpool and he went close on 26 minutes. Borini flicked the ball on with a header and the former Ajax man surged into the area before shooting for the bottom corner, but he could only find the side netting.
Johnson was looking typically effective going forward for Liverpool, but at the back he was as suspect as ever and conceded a free kick in a dangerous area in the final moments of the first period as he brought Odemwingie down from behind, and Liverpool were punished.
Reid's delivery was put behind but, from the resulting corner, the ball was headed out as far as Gera, who half-volleyed a wonderful strike into the top corner of Reina's goal from 25 yards out, and the hosts went into the break ahead.
The second half started significantly quieter, with Liverpool's final ball letting them down, particularly when crossing, and soon West Brom had the perfect opportunity to double their lead.
Long latched on to a clearance and his pace helped him get the better of Daniel Agger, who was forced to bring him down in the area, with the Dane subsequently sent off.
The Ireland striker stepped up for the spot-kick, but his woeful effort was easily saved by Reina to his right.
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Barely three minutes later, however, Long made amends as he won another penalty for the hosts, this time being brought down by Martin Skrtel as he stole the ball from the Slovakian, and Odemwingie buried the kick to make it 2-0.
Following a few crazy minutes and the goal, Liverpool were back in control but still finding it hard to break West Brom down, with their midfield providing virtually no cutting edge and they almost found themselves further behind.
Yacob played the ball forward to substitute Lukaku, who brilliantly spun his marker before marching towards goal with just Skrtel to beat and then, instead of shooting, squared it to James Morrison in the area, but the midfielder skied his effort from 12 yards out.
However, the Baggies did not have to wait much longer before their third goal of the day as Liam Ridgewell dinked a lovely ball to the far post, and Lukaku towered above everyone else to nod in and seal the three points for the hosts with 14 minutes to play.
The young Belgian striker was looking like a man with something to prove following a frustrating campaign last year and he was combining excellently with his new team-mates.
Liverpool continued to press for late goals, even introducing the apparently unwanted Andy Carroll, but they could not find the net and the Baggies recorded an eye-catching victory.