Big Slim, who played in the Rangers' treble-winning side of 1992/93 under Smith, said his former gaffer at Ibrox will have a sense of unfinished business when it comes to the Scotland side.
He called time on his previous stint as national boss after just two years to answer an SOS from Gers following the Paul Le Guen regime.
McPherson reckons with his former gaffer at Hearts, Joe Jordan, also interested, and ex-Scotland team-mate Gordon Strachan the Tartan Army's favoured candidate, it is a case of everyone's a winner when it comes to finding a successor to Levein.
But the 27-times capped former Scotland centre-back, who played every game of the Italia 90 World Cup and 1992 European Championships for Andy Roxburgh, has no doubt that, in the key category of man-management, Smith would be the past master.
McPherson said: "I think we are very lucky to have three guys of the quality of Walter Smith, Gordon Strachan and Joe Jordan.
"All are available for the Scotland job. It is a case of everyone being a winner for Scotland in terms of what they would bring to the table.
"Personally speaking, I would think Walter would be the frontrunner. I would imagine when it comes to Scotland he still nurses a sense of unfinished business after he called time on his spell in charge early to help save Rangers.
"I would also say that when it comes to the Scotland job, the key skill is man-management and getting the best out of the players.
"For me, there is no-one better at that than Walter Smith. I think during the two years he was in charge of the national team we improved around 70 places in the rankings.
"While under Walter we achieved that famous win over the France side who were World Cup runners-up when we won a Euro qualifier 1–0 at Hampden Park.
"Having done it, Walter would be able to come in and pick it up and get things going.
"He is the safest pair of hands there is. So I would make him first choice."
But Mac was also keen to endorse the credentials of Strachan and Jordan.
The former Scotland star said: "I played alongside Gordon in the Scotland team and, tactically, he is very astute. If you look at the fact he has managed Celtic to the last 16 of the Champions League, that is an achievement that grows more impressive every season.
"He also managed at Southampton and Middlesbrough and the only thing missing from his CV is the Scotland manager's job. It might just be that the time is right for Gordon and he is popular with the Tartan Army."
McPherson added: "As for Joe Jordan, you don't get a much more inspirational figure, and no-one was more passionate about playing for Scotland than he was. When he managed me at Hearts, he had just come over from Italy and had so much knowledge and a great way of putting it forward.
"Since then he has assisted Harry Redknapp in the Champions League with Spurs, so when it comes to finding a successor for Craig, the SFA are in a very strong position."
Whoever is appointed will inherit a team which today slipped to 70th in the Fifa world rankings – a drop of 14 places.
Meanwhile, Billy Stark, the interim A squad national coach, will be assisted by Donald Park for next week's friendly in Luxembourg, while Ricky Sbragia takes charge of the Under-21 side for their friendly against Portugal.