She called up 15 of the World Cup-winning group, despite most of the players still being on strike from the national team.
Formerly an assistant to sacked World Cup-winning coach Jorge Vilda, Tome seemed destined for the job one day, but it arrived quicker than expected because of the Luis Rubiales kiss scandal.
Vilda, disliked by some of the players, was dismissed as the Spanish football federation tried to make changes demanded by over 80 players, striking in the wake of former president Rubiales's kiss on midfielder Jenni Hermoso's lips in Sydney.
After Rubiales resigned, 39 players including the vast majority of the World Cup squad, said they still did not plan to return until further changes were made.
However Tome called up many of them, saying she was convinced they would come and hailing their professionalism.
Tome said she left Hermoso out of the squad to protect her. "We are with Jenni on everything, and with all the players," added the new coach.
"The best way to protect her is like this, I have worked five years with her."
Born in the Asturian town of Pola de Siero, Tome, 41, holds the reins of a national team that remains in disarray off the pitch and is exquisite on it.
Tome had been Vilda's deputy since 2018, having started her career playing for Oviedo Moderno in 2003 before moving to Levante in 2007, where she won the league title.
The Asturian midfielder played between 2010 and 2012 at Barcelona, where she won another league before returning to her first club, where she finished her time as a player the following year.
Tome, a runner-up at Euro 2000 with Spain U18s, was capped four times by the senior national team, participating in the qualifiers for Euro 2005.
- 'Different perspective' -
Active on social media and a fan of mountain biking, she worked as a physical education teacher in a primary school after hanging up her boots.
Tome studied a coaching course for former players, where she met the likes of Fernando Redondo, Juan Carlos Valeron and current men's World Cup-winning coach Lionel Scaloni, who is in charge of Argentina.
After obtaining her qualification she joined the Spanish women's national team in 2018 as Vilda's assistant.
"I've always been lucky enough to be able to make a living from football, although when I was a footballer there weren't as many resources as there are now," she said at the time.
"I want to enjoy it as much as possible from a different perspective and live it with them.
"We have a great senior national team, very high level youth categories and we have to make the most of it."
In 2019, the Asturian took charge of the "Absoluta Promesas", a squad between the U19 and the senior team levels, which would later become the U23 team.
Tome combined her duties as Vilda's assistant coach at senior level along with this new position, until she was replaced by Laura del Rio.
In 2020, Tome was assigned the U17 national team, but it became impossible for her to combine it with her work as Vilda's assistant, so she decided to continue with the senior team.
With La Roja she has experienced her best moments, winning the World Cup in Australia and New Zealand in August, but also some bitter ones, including 15 players striking last year over Vilda's methods and working conditions.
The Spain coach was also present at Rubiales' speech during which he refused to resign, and she offered to step down from her post the following day, along with the majority of Vilda's coaching staff.
She said on Monday when naming her squad for the Nations League matches she was only applauding certain elements of the speech.
"It's true I worked with Vilda for five years, but I'm not Jorge Vilda," said the coach.
"I'm Montse Tome, I'm a different person with a different personality and different values. All the players know me and I know what they think and feel about me."
Now Tome is setting her sights on further achievements, including a potential Olympics appearance in 2024, but chaos still reigns around her.