In a single IF..ELSE statement, if the expression evaluates to True in the IF statement the control enters the first BEGIN..END block and only the code inside that block gets executed , Else block is simply ignored.
On the other hand if the expression evaluates to False the ELSE BEGIN..END block gets executed and the control never enters the first BEGIN..END Block.
In the Example below the expression will evaluate to false and the Else block will be executed printing the string 'First expression was not true'
IF ( 1 <> 1) --<-- Some Expression
BEGIN
PRINT 'One is equal to One'
END
ELSE
BEGIN
PRINT 'First expression was not true'
END