Roland Chlapowski, a long-time Swiss Life employee appointed to the role in February, will leave immediately, the insurer said.
The shake-up follows two restatements of accounts within a month, and an admission that six executives made profits of 11.5m Swiss francs through a company investment vehicle.
The vehicle, Long Term Strategy, allowed senior staff to invest in some of Swiss Life's deals.
Mr Chlapowski's departure also comes ahead of an attempt to raise SFr1.2bn from investors.
Lost confidence
Swiss Life has, like many other insurers, sought to raise cash to cover liabilities, following a rash of recent claims.
The company will seek to sell new stock, at a discount, to existing shareholders - undertaking a so-called rights issue.
But fears have grown that investors would be deterred by the insurer's recent troubles.
"The board of directors is aware that confidence has been lost, partly because of the accounting errors but also because of the debate over LTS," chairman Andres Leuenberger said.
"It is vital to reinforce customers' and investors' faith in Swiss Life again, and quickly, as well as the confidence of the authorities and the general public."
Mr Chlapowski is being replaced by banking industry veteran Rolf Doerig, previously chairman Switzerland for Credit Suisse Group.
"[Mr Doerig] possesses the necessary integrity to put our company's relationships with all our partners on a new basis of trust," Mr Leuenberger added.
Investor reaction
Many observers reasoned that Mr Chlapowski's departure would boost the chances of the rights issue succeeding.
Others pointed out that Wednesday's reshuffle was the third within a year.
"I think [Swiss Life] will muddle through and finally get money but this won't be without difficulties," said Claude Zehnder, market analyst with Zuercher Kantonalbank.
Swiss Life shares surged 14% in early trade before closing up 7.6% at Sfr163.50.
The stock is, nonetheless, down almost 80% on the year.