Sky Blues coach Frank Farina on Wednesday unveiled Del Piero as his side's new skipper, replacing foundation player Terry McFlynn after three seasons at the helm.
"I'm very happy and I will give everything - from my knowledge and experience - to have my team win the title, to fight in the play-offs and to be the best team in Australia if it's possible," Del Piero said.
"Terry was a great captain and it was a pleasure to play for him last season.
"I hope to have the same backing and respect as Terry had from the players.
"I want to do my best ... to help the team in every single situation - inside the dressing room, outside the dressing room and especially on the field.
"Only together we can win a game, only together we can win a title."
Del Piero held the vice-captaincy with Brett Emerton last season, donning the armband when McFlynn did not play or was substituted off.
The 38-year-old Italian attacker scored 14 goals in 23 games for Sydney FC - the most since his 2007-2008 season with Juventus, when he scored 21.
'Alessandro is a role model in the dressing room and is highly respected amongst the players at the club," Farina said.
'He has already shown his leadership qualities since being here, helping out the younger players and becoming a major influence within the team."
With a swag of new signings and departures, the Sky Blues are set to field a considerably different line-up to last season when they kick off their 2013-2014 campaign against Newcastle on Friday 11 October at Allianz Stadium.
Sydney will be without the likes of departed Lucas Neill and Joel Griffiths and injured Terry Antonis, but welcome back Nick Carle from his loan deal to Baniyas, Pedj Bojic from defending champion Central Coast Mariners and Brisbane Roar's Matthew Jurman - among others.
"Last year is last year. It's part of the past. We have to think about last year only to understand what is wrong and what we think we can do better," Del Piero said.
"But that's not what will happen this year, for sure.
"We changed a lot of players. Frank is head coach from the start of the season, not half-way (through) like last year.
"That has changed a lot - because with him, and the coaching staff, we can spend time on the field to understand each other."
Sydney FC's rounds off its pre-season campaign with games away to Brisbane Roar (22 September in Cairns) and at home to Perth Glory (29 September.