We present the performance characteristics of a time-of-flight secondary ion mass spectrometer designed for 157 nm laser postionization of sputtered neutrals for high sensitivity elemental and isotopic analyses. The instrument was built with the aim of analyzing rare element abundances in micron to submicron samples such as interstellar grains and cometary dust. Relative sensitivity factors have been determined for secondary ion mass spectrometry which show an exponential dependency against the first ionization potential. This allows elemental abundances to be measured with errors below 25% for most major elements. The accuracy for isotope ratios, where isotopes can be resolved from isobaric interferences, is usually limited only by counting statistics. In laser secondary neutral mass spectrometry, the spatial and temporal overlaps between the laser and sputtered neutral atoms are modeled and predictions of total detection efficiency and isotopic and elemental fractionation are compared with experimental data. Relative sensitivity factors for laser-ionized secondary neutrals from a stainless steel standard are found to vary less than 3% above saturation laser pulse energy enabling more accurate quantification. © 2007 American Institute of Physics.