The Blues have taken more points from opening-day fixtures than any other side in the top-flight and host Steve Bruce's newly-promoted Tigers in search of another win on Sunday
The Portuguese enjoyed a highly successful first stint at the club, with his three-year stay yielding two Premier League titles, an FA Cup and two League Cup triumphs.
He is the man charged with bringing the Premier League crown back to Stamford Bridge for the first time since Carlo Ancelotti achieved the feat in 2009-10.
The club have made several additions during the close-season, including forward Andre Schurrle from Bayer Leverkusen, goalkeeper Mark Schwarzer from Fulham and midfielder Marco van Ginkel from Vitesse.
And Dutchman Van Ginkel is itching to be involved against Hull.
"I'm looking forward to the first game," the 20-year-old told the club's official website. "I'm hoping to be involved against Hull City and it will be nice for me to go to Stamford Bridge.
"If we win the first couple of games, which are both at home, it puts us in a very good position going into a big game away at Manchester United, but for now our focus is only on putting in a good performance against Hull."
Mourinho has no injury or suspension worries ahead of the game and he could decide to feature Belgian attacking duo Romelu Lukaku and Kevin de Bruyne, who had loan spells at West Brom and Werder Bremen respectively last season.
Hull's return to English football's top table was secured in dramatic fashion on the final day of the Championship season, when a 2-2 draw against already promoted Cardiff City proved to be sufficient to take second spot as Watford succumbed to a 2-1 defeat at home to Leeds United.
Manager Steve Bruce has wasted no time in building a side that he feels is capable of achieving Premier League survival, with no less than 10 signings during the current transfer window.
And the former Wigan Athletic manager is delighted with the business he has completed, though he warned that retaining Hull's top-flight status will be no easy feat.
"Overall, I'm delighted with what we've done," he told BBC Radio Humberside. "I've managed to get in all of the players who were at the top of my shopping list.
"We've got to stay up but when you look at it 47 teams have competed in the Premier League in the last 22 years and only eight have been there all the time."
Bruce heads into the game without former Sheffield United midfielder Stephen Quinn, who will miss the game with a hamstring injury that he sustained in a pre-season fixture with German outfit Eintracht Braunschweig.
History points to a home victory, with Chelsea leading the head-to-head record between the two clubs by 19 wins to Hull's four.
Chelsea have also taken more points from opening-day fixtures than any other team in the Premier League era, with an impressive haul of 44.