This paper reports on the advanced development of an ultrasensitive method for the detection of benzene, toluene, and ethylbenzene (or BTE) by low-pressure photoionization mass spectrometry (LPPI-MS). The LPPI source is composed of a laboratory-assembled krypton lamp and a stainless steel cylindrical ionizer. A compact V-shaped mass spectrometer is coupled to the LPPI source with a set of ion immigration optics under dc bias. The fixed standard concentration (FSC) and fixed standard volume (FSV) method are employed to calibrate the sensitivities of the instrument. The corresponding detection sensitivity toward BTE is 4-7 counts/pptv and the 2σ limit of detection (LOD) is 0.5-0.8 part per trillion by volume (pptv). In addition, the measurement accuracy is 95%-105%, and the corresponding precision ranges from 3% to 15% and from 9% to 31% for the FSC and FSV methods, respectively. The stability (standard deviation) of LPPI-MS for a 1 ppbv BTE mixture is less than 0.025 (>12 h). In the detection of BTE, water in ambient air is the most significant interfering factor, leading to the increased background, and inferior LODs of 1-2 pptv for BTE under an RH of ∼90% is observed. Experimental results indicated that LPPI-MS is reliable for the detection of sub-pptv levels of BTE under laboratory conditions.