AbstractApplication of a laser ion source (LIS) is a promising new technique for trace analysis with high efficiency and selectivity. One of the problems which can limit its efficiency attained in practice is the adsorption of sample atoms on the hot walls of the LIS cavity. We have studied the release of atomic technetium from different wall materials at temperatures up to 2500 K. For these investigations resonance ionization of technetium atoms applying a copper vapour pumped dye laser system and γ‐spectrometry of 6‐h99mTc have been used. Theoretical calculations of the heat of desorption for technetium on different wall materials are presented and compared with experimental data. Though the results reported concern technetium, most of the considerations are quite general for a laser ion so