Woolmer, now in charge of Pakistan, is backing Michael Vaughan's side to claim England's first series win in South Africa since 1964/65 and believes Smith's leadership could be the hosts Achilles heel.
"Where there was once praise for the captaincy of Graeme Smith, there are now question marks," Woolmer writes in the December issue of The Wisden Cricketer.
He added: "On top of that, the mental fatigue that the South Africans are going through is vastly greater than that of England.
"The New Zealand captain Stephen Fleming put Smith under severe verbal attack earlier this year, deliberately exploiting his emotional rawness, but Michael Vaughan will not even need to do that: there is more than enough pressure on Smith right now."
Woolmer had nothing but praise for Vaughan, who has helped transform England into one of the form teams of world cricket.
"Michael Vaughans captaincy has been transformational. The team is focused, determined, skilfully led, and well managed. He is a firm, popular and clever leader. He has the same grit displayed by other Yorkshire captains: a combination of Len Hutton, Ray Illingworth and Brian Close."
Woolmer believes fast bowler Steve Harmison could prove to be England's match winner.
"He will be a major difference so long as the England management can ensure that he travels well, which has not always been the case.
"He poses a genuine threat with his pace and bounce, especially on some of the South African pitches, and if he targets Smith as he did Brian Lara in the Caribbean he could achieve the same result.
"South Africas pace attack, by contrast, is a shadow of its former self. Shaun Pollock is wiser but slower and Makhaya Ntini is as willing as ever, but the rest are only just better than ordinary."
Worryingly for the South Africans, Woolmer's damning verdict was endorsed by one of their own, the legendary Allan Donald.
"At the moment England probably have the best seam attack in the world. But the South African hierarchy are extremely worried about where they are going to get bowlers from. Our attack is lacking penetration, punch and pace," Donald admitted.