SQL Server IF NOT EXISTS Usage?

Have you verified that there is in fact a row where Staff_Id = @PersonID? What you’ve posted works fine in a test script, assuming the row exists. If you comment out the insert statement, then the error is raised.

set nocount on

create table Timesheet_Hours (Staff_Id int, BookedHours int, Posted_Flag bit)

insert into Timesheet_Hours (Staff_Id, BookedHours, Posted_Flag) values (1, 5.5, 0)

declare @PersonID int
set @PersonID = 1

IF EXISTS    
    (
    SELECT 1    
    FROM Timesheet_Hours    
    WHERE Posted_Flag = 1    
        AND Staff_Id = @PersonID    
    )    
    BEGIN
        RAISERROR('Timesheets have already been posted!', 16, 1)
        ROLLBACK TRAN
    END
ELSE
    IF NOT EXISTS
        (
        SELECT 1
        FROM Timesheet_Hours
        WHERE Staff_Id = @PersonID
        )
        BEGIN
            RAISERROR('Default list has not been loaded!', 16, 1)
            ROLLBACK TRAN
        END
    ELSE
        print 'No problems here'

drop table Timesheet_Hours