If you're going to use absolute positioning you need to do it like this:
#highlight_lose {
width: 550px;
height:550px;
position: absolute;
top: 50%;
left: 50%;
margin: -225px 0 0 -225px;
display: none;
}
Edit: you also need to add position:relative;
to the main div. Here is an updated fiddle.
http://jsfiddle.net/FragJ/2/
It looks off because you have other elements that aren't exactly centered.
EDIT: As I stated earlier, the smiley didn't look centered because your code is off. The maze really should be inside a div itself. However I was able to eyeball center it simply by playing with the margins.
http://jsfiddle.net/FragJ/4/
To achieve this you'll need to set your css like this:
#main {
position: relative;
width: 550px;
height: 550px;
float: left;
margin-left: 220px;
margin-top: 100px;
background: grey;
overflow: hidden;
}
#highlight_win {
width: 550px;
height: 550px;
position: absolute;
top: 50%;
left: 50%;
display: none;
margin: -180px 0 0 -180px;
}
#highlight_lose {
width: 550px;
height:550px;
position: absolute;
top: 50%;
left: 50%;
margin: -180px 0 0 -180px;
display: none;
}