The construction and performance study is reported for a newly developed ultraviolet photoionization ion mobility spectrometry (UV-IMS). In the present paper, an UV-IMS technique was firstly developed to detect eleven isomeric volatile organic compounds including the differences in the structure of carbon chain, the style of function group and the position of function group. Their reduced mobility values were determined and increased in this order: linears < branches < cycles, primary < secondary < tertiary, para- < meta- < ortho- and alcohols < acetones < aromas. The concentrations of analytes were obtained by means of exponential dilution method, and the experiments show that the limit of detection of the homemade UV-IMS was around ppb-ppm.