Milan launched their campaign with a 1-0 victory over Sampdoria at the Luigi Ferraris Stadium, where Brahim Diaz netted the decisive goal after just nine minutes on Monday.
Pioli handed a debut to new signing and goalkeeper Mike Maignan, while Olivier Giroud also made his bow in the absence of injured talisman Zlatan Ibrahimovic up front.
Despite injury ruling out Franck Kessie, Rade Krunic produced an assured performance in midfield and there was no change allowed from the central defensive pairing of Simon Kjaer and Fikayo Tomori – the pair helping the Rossoneri keep a sixth consecutive clean sheet, their longest run without conceding in the league since February 1994.
Having finished 12 points behind rivals and champions Inter last season, Milan – who have won 11 away Serie A fixtures since the start of 2021, the joint-most in the top-five European leagues, alongside Manchester City and Barcelona – are aiming to go one step better this term and claim a first Scudetto in 11 years.
Milan head coach Pioli is encouraged by the competitive nature and depth within his squad following matchday one.
"I'm happy to have won and to have chased the second goal," he told Sky Sport Italia.
"I like how the team interpreted the game. We have always looked for the goal and this is the right mentality.
"Aside from [Franck] Kessie's injury, I knew we had prepared well.
"We are becoming a strong team with a lot of competitiveness in the group. We know so many ways to play.
"There's a lot of balance now. I don't like limitations. I know I coach a strong team. Just think of the players who were out tonight.
"Maybe the right word is ready; this is the most ready Milan."