An alcohol-thermal route has been developed to the growth of single crystals of yellow metastable PbO in largest dimensions of 11 x 1 x 0.1 mm(3), using freshly synthesized beta-PbO crystallites as seeds. The transformation of metastable P-PbO to stable form (alpha-PbO) can be slowed down by choosing appropriate solvent as the growth medium. The obtained P-PbO crystals have a strong orientational growth parallel to the (0 0 1) plane and exhibit a lath shape. Studies found that cooling rate and NaOH concentration also have great influence on the crystallographic forms of the final products during the alcohol-thermal process. (c) 2005 Elsevier B.V. All rights reserved.