The Portuguese has made a habit of securing league crowns in his second season in any given post – building that record in spells at Porto, Chelsea, Inter and Real Madrid.
He delivered three trophies to United in his debut campaign at Old Trafford, but could only finish sixth in the league.
Neville believes a dramatic improvement will be made in 2017-18, with the Red Devils favourites to restore domestic dominance in the English top-flight.
The former United star told the Premier League’s official website: “The two Manchester clubs will fight it out for the league, but Jose Mourinho’s track record of winning titles in his second season and the buys they’ve made this summer mean I am going for United.”
Mourinho has spent big this summer bolstering his ranks, with Victor Lindelof and Nemanja Matic bringing added steel to the Red Devils.
Romelu Lukaku, a proven Premier League goalscorer, has also been acquired for £75 million and Neville believes he could be the man to inspire a title bid.
Pressed on who he expects to land the Golden Boot, Neville said: “Either Harry Kane or Romelu Lukaku. I can’t choose between the two!
“Lukaku will get chances, which, if he converts them, will land Man Utd the league.”
Kane pipped Lukaku to the top goalscorer gong in 2016-17, as he wrapped up back-to-back successes.
He may, however, find the going a little tougher next season, with Neville suggesting that Tottenham could be the side to miss out in what promises to be another intriguing tussle for the top-four.
He said: “I think playing at Wembley will be a major challenge for Tottenham Hotspur. The big wide open pitch will be totally different to White Hart Lane.”
The new Premier League season gets underway on August 11, with United opening their campaign at home to West Ham on August 13.