The invention relates to a no-standard-sample analysis and detection method of polymethoxydimethyl ether product system. The no-standard-sample analysis and detection method comprises the following steps: by utilizing a gas chromatography-hydrogen flame ionization detection technology, adopting an internal standard method, and adopting a relative response factor derived and obtained by a relationship between relative response of a substance to be detected in an FID (Flame Ionization Detector) and a molecular structure thereof, detecting the contents of methyl alcohol and polymethoxydimethyl ether DMMn in the product system. Compared with the prior art, the no-standard-sample analysis and detection method has the advantages that a high-purity standard sample for detection is not needed, a working curve does not need to be calibrated before the sample is detected, and the economic cost and the time cost in analysis are low; simultaneously, the relative response factor used as the basis of the method is from theoretical calculation and is not influenced by errors of experimental determination, the analytic accuracy is high and the result is reliable.