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Magnetophotoluminescence spectroscopy of unintentionally doped thin CdTe/͑Cd,Mn͒Te single and double quantum wells ͑QW's͒ revealed a pronounced excitonic transition that can be associated with either an exciton bound to a neutral donor (D 0 X) or a negatively charged exciton (X Ϫ ). Comparative experimental study and theoretical analysis of this transition in quantum wells of different thicknesses allowed us to attribute it to the D 0 X complex in a single QW and to the X Ϫ state in the double QW. A record X Ϫ binding energy of 3.7 meV has been detected. The double QW structure was shown to be favorable for the formation of X Ϫ in the wide well due to the efficient interwell electron tunneling. ͓S0163-1829͑98͒05431-9͔ PHYSICAL REVIEW B 15 AUGUST 1998-I VOLUME 58, NUMBER 7 PRB 58 0163-1829/98/58͑7͒/4082͑7͒/$15.00 4082