The 26-year-old forward, who has been on the Baggies' radar for several years, has been threatened with exile to the PSV reserves after refusing to discuss a contract extension with the Dutch club.
And that is likely to interest the Baggies, who are long-standing admirers of the Sweden international. Toivonen, who can play up front, as an attacking midfielder or as a winger, is open to the idea of moving to England.
He shares an agent – former Sweden striker Martin Dahlin – with current Hawthorns players Jonas Olsson and Markus Rosenberg.
PSV want to recoup the £3.75million they paid Malmo for his services in 2009 but, with Toivonen entering the final year of his contract, the asking price is likely to come down.
West Brom have watched Toivonen for several years and considered a bid in 2011 during his previous contract talks with PSV.
But the Baggies, who had survived just one season in the Premier League at the time, were a less attractive proposition while the Dutch side's asking price of around £8million ruled them out.
Toivonen eventually signed a new three-year deal at PSV but has now decided he will run down his contract, which expires next summer, upsetting PSV coach and former Holland midfielder Phillip Cocu.
The former Orgryte player, who is also believed to have been watched by Everton, claims he has been told he will be banished to the reserves if he does not sign a new deal by the start of July.
But he appears ready to stick to his guns, meaning PSV are likely to try to cash in.
Toivonen boasts an impressive record of 48 goals in 100 appearances for PSV in all competitions.
The player, who is currently on international duty with Sweden, said: "On July 1 I will go to the B team to train. I do not intend to sign a new contract so I will be on the B-side team.
"I feel it's poor respect from the club. I have already signed a contract with them and extended it once.
"So yes, I think it's poor respect."