An overview is presented on the power and drawbacks of the relatively unfamiliar chemiluminescence-based detection technique applied in analysis by capillary electrophoresis, for determining chemically derivatized biomolecules. Examples of the most common systems are given for many series of biologically active compounds as well as for some pharmaceuticals. The most common chemiluminescent systems include the application of peroxyoxalate ester chemiluminescence, acridinium esters, luminol and derivatives, detection based on the tris(2,2'-bipyridine)ruthenium(III) system, the huge potentials offered by direct oxidations-though often with still unelucidated reaction mechanisms-and the powerful area of bioluminescence techniques, revealing as well the fast developing area of microchip-based analysis employing this specific luminescence principle.