Tetra-hydrothiophene ((CH₂)₄S) has an odor that is detectable at very low levels. For this reason, it was included as a component of dangerous gases to allow the detection of leaks by smell. A type of tetra-hydrothiophene gas CRM in the μmol/mol level was developed for the analysis of trace-level odorant gas in natural gas. The gas standards produced simultaneously in 3 bottles and examined by GC-FID were show with 0.12%, reproducibility of preparation and 0.05%, standard uncertainty due to weighing and purity. The concentration of tetra-hydrothiophene ((CH₂)₄S) was 10 µmol/mol level in the cylinder filled with methane, 1500 psi. And the variability of concentration for 1 years was about 0.03% due to the adsorption or instability of (CH₂)₄S. The relative expanded uncertainty of 1.0% (95% of confidence level, k=2) was assigned to the certified value of 10 μmol/mol level of(CH₂)₄S after quantitative evaluation on the purity, mixing, weighing, analysis, adsorption and stability of tetra-hydrothiophene gas.