A laser microprobe and resonance ionization mass spectrometer (LAM/RIMS) has been designed and constructed by combining a newly designed simple laser microprobe (LAM) with a continuous‐wave (cw) resonance ionization mass spectrometer, for the direct analysis of trace elements in solids. The LAM/RIMS has achieved a simultaneous record of the complete mass spectrum of a solid sample, and a three orders of magnitude enhancement in the detection signal of the selected trace elements in the solid, with precise spatial information, and without the need of sample preparation. An‐type silicon wafer containing an impurity of sodium in parts per billion order has been easily detected by applying a single shot of an ablation laser pulse and a cw resonance ionization laser. The result has also shown that the sensitivity of the LAM/RIMS for the analysis of selected trace elements is better than the Auger electron spectroscopy and is comparable to neutron activation analysis.