Volume concentration determination for atmospheric krypton and xenon is very important for krypton-85 and radioactive xenon isotopes monitoring. An injection setup integrated adjustable quantity sample injection and quantitative dilution function was designed. The effects of EI source parameters on the sensitivity of MS detector were studied. The optimized values were as following: ionization energy of 70 eV, emission current of 40 mA, cathode voltage of 27 mV, focus voltage of 85 mV and lens compensation of 20 V, respectively. A GC-MS method for the determination of krypton and xenon in atmosphere without of sample pretreatment was developed. The minimal detected concentrations for krypton and xenon were 3. 3×10-8(V/V) and 2. 6×10-9(V/V). Moreover, the krypton and xenon concentrations in the ground level air around our laboratory were measured with the results of 1 . 1 × 10-6 ( V/V ) and 9 . 3 × 10-8 ( V/V ) . The related combined standard uncertainties for krypton and xenon results were 2. 38% and 3. 15%, respectively.