He steps in after regulators shuttered the startup-focused lender on Friday after a run on its deposits that left it with a dearth of capital.
Mayopoulos served as the chief executive officer of mortgage financier Fannie Mae for more than six years before he joined fintech Blend.
The collapse of SVB, the biggest bank to fail since the financial crisis of 2008, has crippled stocks and triggered concerns of a contagion throughout global markets.
Last week, the bank failed to raise capital to plug a $1.8 billion loss from the sale of a $21 billion portfolio of available-for-sale securities that triggered massive deposit outflows.
The regulator has also transferred all deposits – both insured and uninsured – and substantially all assets of the bank to a newly created bridge bank.