The teams from the capital and the country's second largest city won all the national league titles in the last eight years between them, with Maribor claiming six and also playing in the Champions League in the last season for the second time.
They had the same number of points last year, with Olimpija winning on account of a better head-to-head record.
Things have been tense in both clubs in the past year, but while Maribor ironed out their differences with "enfant terrible" football director and former great Zlatko Zahović, Ljubljana parted ways with coach Igor Bišćan.
Bišćan and Olimpija failed to come to an agreement even though the former had helped the team win the national as well as the cup title. Ljubljana, coached now by Serbian expert Ilija Stolica, also let go some of its key players and was eliminated in the first round of qualifying for the UEFA Champions league last week.
The two main favourites, who will first clash on 18 August, have however had noteworthy challengers in recent years, especially Domžale, who played a stellar second part of the last season to finish third.
Velenje and Celje are also being handled as potential surprises, while the hopes are also high in the very north-east of the country, as Mura from Murska Sobota, once a top club, have returned among the ten teams making up the Slovenian football premier league after a five-year break.