In web.config, you can add multiple connection strings as follows:
<connectionStrings>
<add name="connStr1" connectionString="server=localhost;database=yourDb;uid=yourUser;password=password;" />
<add name="connStr2" connectionString="server=localhost;database=yourDb;uid=yourUser;password=password;" />
</connectionStrings>
For reading, use the following code:
string connStr1 = ConfigurationManager.ConnectionStrings["connStr1"].ConnectionString;
string connStr2 = ConfigurationManager.ConnectionStrings["connStr2"].ConnectionString;