For the first time NaCu2O2 single crystals were prepared by a self-flux technique in Pt crucibles. The as-grown crystals have typical dimensions of 7 x 3 x 0.1 mm(3). Powder and single crystal XRD measurements confirm the high quality of the prepared crystals. All crystals have the orthorhombic structure: a = 6.2087(1) Angstrom, b = 2.9343(1) Angstrom and c = 13.0648(3) Angstrom. DTA-TG and high-temperature optical microscopy studies show that the NaCu2O2 compound is stable in the temperature range 25-760degreesC and melts incongruently at 905+/-5degreesC in argon atmosphere. Magnetic susceptibility measurements carried out on the single crystals showed clear evidence of antiferromagnetism at T-N = 12.25 K. (C) 2003 Elsevier B.V. All rights reserved.