This Letter reports probing of non-ionic, anionic and cationic micelles utilizing different dual emission properties of 4-(N,N-dimethylamino) cinnamaldehyde. Twisted intramolecular charge transfer (TICT) band is more enhanced and blue shifted in non-ionic micelle than those are in ionic micelles. In non-ionic micelle, the molecule enters in the core region whereas, in ionic micelles, it is anchored in the interfacial region with different orientations. Micellar-water interface electric field in ionic micelles was found to have profound effect on TICT decay time. Interestingly, inorganic salt-counterion binding helps the acceptor moiety to enter into the core region in anionic micelle. (C) 2002 Elsevier Science B.V. All rights reserved.