The round of 16 match was played at the brand new Al Janoub Stadium built for the 2022 World Cup.
It saw Spain and Barcelona legend Xavi helming Al Sadd after ending his playing career with the 2011 Asian champions a couple of months ago.
Xavi's last domestic game was also against Al Duhail in the final of the Amir Cup, but it ended in huge disappointment as Al Sadd, who had won the Qatar Stars League a few weeks earlier, crashed to a stunning 4-1 defeat.
Tuesday's continental clash was thus a great opportunity for some measure of revenge and although it didn't materialise, Al Sadd would still be the happier team, having scored a vital away goal before the return leg at the Jassim bin Hamad Stadium next week.
Al Sadd began with plenty of spirit with Akram Afif particularly impressive up front, while Al Duhail saw their Moroccan star Mehdi Benatia hobble off with an injury after just 18 minutes.
Bassam al-Rawi, who replaced Benatia, made an immediate impact, his first touch off a free-kick sailing over the crosspiece.
Al Duhail had a golden chance to score in the 24th minute but Ali Musa's headed effort from a corner was thwarted by Al Sadd goalkeeper Saad al-Sheeb.
The deadlock was finally broken on the half-hour mark by Akram Afif after Mohamed Muntari's attempted long clearance was intercepted by Jung woo-Young in the midfield.
The Korean was quick to pass the ball to Afif on the left edge of the box and the striker evaded a defender to score with a low shot into the left corner of the net past goalkeeper Amine Lecomte.
The next few minutes saw both teams playing cautiously while looking for openings, with Al Duhail finding one just a minute before half-time.
Brazilian Edmilson found space on the right and moving up crossed the ball into the box where Muntari chested it down for Yousef Msakni to score with a half-volley in the 44th minute.
Msakni, who spent the entire last season nursing an injury, even missing the World Cup for Tunisia, was playing his first match for Al Duhail after a short spell at Qatar-owned Belgian club Kas Eupean as part of his rehabilitation.
Al Duhail controlled the match in the second half, but missed a couple of potential chances with Almoez Ali, and al-Rawi accounting for them.
In the second match of the day, Bafetimbi Gomis scored a hat-trick as Saudi Arabia's Al Hilal rallied from an early goal deficit to beat domestic rivals Al Ahli 4-2 in Jeddah.
Syrian star Omar al-Somah had given Al Ahli the lead in the sixth minute from an assist by Abdulfattah Asiri, but Gomis struck in the 15th to restore parity
But after Jorge Djanini of Cape Verde had put Al Ahli ahead for the second time in the 39th minute, Al Hilal hit back with two goals from Gomis in the second half to gain the upper hand.
Abdulla al-Hafith then added an 81st minute goal to help the 1991 and 2000 Asian champions take a healthy two-goal advantage into the second leg which they will play at their home ground.