SELECT
i.*,
r.name AS roomname,
c.name AS cat,
p.key AS imgkey,
p.extension AS imgext
FROM
items i,
rooms r,
Since your Items.Room = the Rooms.Key, I would just have that as the where..
SELECT
i.*,
r.name AS roomname,
c.name AS cat,
p.key AS imgkey,
p.extension AS imgext
FROM
items i
LEFT JOIN photos p
ON p.referencekey = i.key
JOIN rooms r
on i.room = r.key
JOIN categories c
on i.categorykey = c.key
WHERE
i.sitekey = 32201
AND i.room = 663308