Efficient emission of positronium negative ions from Cs deposited W(100) surface has been observed. The emission efficiency measured over a time interval of 3000 s immediately after the deposition was found to be 1.25% for the target with a 2.2 × 1014 atoms/cm2 Cs layer. The emission from Cs deposited polycrystalline Fe surface has also been observed. The upper limit of the binding energy of the ion has been estimated experimentally. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)