Owners of mission-critical applications are more likely to turn to commercial products like Oracle, SQLServer etc to ensure reliability, performance, support and functionality.
Here are some interesting stats though:
Cox Communications uses MySQL to manage information related to its cable modem business.
NASA uses MySQL to store information about public contracts.
Slashdot, a widely read online publication, uses MySQL to store all of the information related to its site.
The Associated Press uses MySQL to serve various types of information, including access to the U.S. Census and Olympic results.
Afilias, which manages the .ORG registration, uses PostgreSQL to store all of .ORG registry information.
The American Chemical Society uses PostgreSQL to store documents that exist only within that database.
BASF uses PostgreSQL in a shopping platform for its agriculture products.
The World, a media company, has built much of its infrastructure around the use of PostgreSQL.