La Viola only missed out on a Champions League place on the final day of the 2012-13 campaign as AC Milan got the result they needed to finish third, but the Tuscans look much stronger heading in to the new season after landing several high-profile players.
Experienced midfielder Massimo Ambrosini rejected overtures from West Ham to sign a one-year deal in Florence while Josip Ilicic, Joaquin and Juan Cuadrado will add further creativity to what was already a fluid attacking system.
Most impressive, however, has been Montella's surprise capture of striker Mario Gomez, who arrived at the Stadio Artemio Franchi for 16million euros after scoring 113 goals in four years with Bayern Munich.
The German will likely partner Giuseppe Rossi against Catania on Monday night. The Italy regular has fully recovered from ligament damage sustained at former club Villarreal.
Montella told Fiorentina's official website: "No one here has asked me to win the league. Our aim is to try and repeat what we did last term: to play good football and to get back into Europe.
"We're a different team to the one that finished last season. We're at the start of a new journey."
Ambrosini serves a one-match ban against Montella's former club while defender Ahmed Hegazy and midfielder David Pizarro miss out due to injury.
The Sicilians will be without injured Argentinian duo Gino Peruzzi and Sergio Almiron but new recruit Panagiotis Tachtsidis is ready to plug the gap in midfield left by free-kick specialist Francesco Lodi, who has joined Genoa.
Montella added: "Catania did some great work with (coach Rolando) Maran last year and were the surprise package of the season.
"They may have lost Lodi but they have a stronger physical presence now with Tachtsidis in the side."
Maran's men are eager to build on their best-ever Serie A season by improving on an eighth-placed finish.
While veteran defender Nicola Legrottaglie is unimpressed with kicking off that bid on a Monday night - a necessary move given Fiorentina's European commitments - he feels the switch could work against the hosts.
"There's no advantage or disadvantage, but I imagine there will be a great sense of anticipation," he told La Repubblica Sport.
"They will either be fired up to give us a good game or they could be suffering from first-day-of-school nerves.
"So we must have absolute conviction in what we do."