Alain Perrin enjoyed a dream start to his Portsmouth career as his side saw off Charlton in a cracking match.
Pompey started superbly as Yakubu headed in Steve Stone's cross inside three minutes, before Stone netted with his own header on 19 minutes.
But Jonathan Fortune headed a goal back and Danny Murphy's fine free-kick drew Charlton level before half-time.
Yakubu hit a post but Diomansy Kamara's 83rd-minute header put Pompey ahead, before LuaLua netted the fourth.
It was a deserved winning start for Perrin who saw his side adopt an adventurous approach from the outset.
But even he cannot have envisaged the brilliant beginning which saw his side ahead after just 130 seconds with Yakubu's header.
Shaun Bartlett's 15th-minute shot came within inches of bringing Charlton level, but his right-foot shot curled just wide with Jamie Ashdown beaten.
It looked like Charlton would regret the miss as Stone headed his side two goals up on 20 minutes from Patrik Berger's cross.
But the mood at Fratton Park quickly changed from jubilant to nervous as the Addicks found themselves back in the match just 40 seconds later.
Fortune rose above the napping home defence to head home Murphy's cross from a free-kick.
And the home fans' worries proved well-founded as, in first-half injury-time, Charlton drew level, once again thanks to Murphy's dead-ball skills.
Ashdown was motionless as the ex-Liverpool man's well-struck free-kick curled around the wall and into the net.
A delightful one-two between Giannis Skopelitis and Yakubu nearly resulted in Pompey re-taking the lead shortly after the break, but the Nigerian striker blazed over.
The home side came even closer as Skopelitis blasted the ball goalwards after a scramble, but Hermann Hreidasson blocked the ball.
Referee Graham Poll waved away Pompey players' appeals for a penalty, judging that the ball had struck the Charlton player's chest, not his arm.
Still Portsmouth attacked, and Kiely saved well from LuaLua before Yakubu's right-foot volley hit the post.
Nevertheless, Charlton threatened sporadically and Murphy's quick free-kick forced a diving save from Ashdown on 70 minutes.
But just as it looked like a draw was looming, substitute Kamara popped up to head home LuaLua's right-wing cross.
And Lua Lua had the final say, with a smart injury-time finish.
New Portsmouth boss Alain Perrin:
"We're all happy, the chairman, the players, the fans, everybody.
"It's a good win to begin with and there were four goals. It was exciting. I wasn't worried that having been two goals ahead we were back to 2-2.
"I think the benefit of me was mainly psychological. The players responded to a new manager."
Charlton boss Alan Curbishley:
"The way the goals went in was not very good, but Portsmouth are a decent side. I saw them against Fulham and they did well..
"I'm afraid the stats show this is what we do. We're letting in too many goals.
"I changed things and went with a nice solid 4-4-2 but we were a goal down in two minutes. When we came back to 2-2 we wanted to give ourselves a base."
Portsmouth: Ashdown, Cisse, De Zeeuw, Stefanovic, Taylor (Primus 80), Stone, Skopelitis (Kamara 60), Hughes, Berger (Rodic 72), Yakubu, LuaLua.
Subs Not Used: Chalkias, O'Neil.
Goals: Yakubu 3, Stone 20, Kamara 83, LuaLua 90.
Charlton: Kiely, Young, Perry (Johansson 88), Fortune, Hreidarsson, Kishishev (Thomas 19), Holland, Murphy, Konchesky, Jeffers, Bartlett (Lisbie 61).
Subs Not Used: Hughes, Andersen.
Booked: Murphy, Hreidarsson, Perry.
Goals: Fortune 22, Murphy 45.
Ref: G Poll (Hertfordshire).