Regioselective di- and tetrabrominations of the (B,O)2-perylene 1 afford derivatives 2-4. Despite their poor solubility, 2 and 4 could be used in Stille-type coupling reactions to introduce two CCMe (5) or four CC(p-C6H4tBu) substituents (6), respectively. The alkynylated derivatives show blue-green photoluminescence with appreciable quantum efficiencies.