An experimental device for the polarization scattering of aerosol single particles is developed. The T-matrix method is used to simulate the light scattering calculation of spherical particles and long particles. The relationship between polarization intensity factor (Pf), Müller matrix elements (Z11 and Z12) with particle size and shape is discussed. The results show that, with the increase of particle size, there are significant differences between spherical particles and rod-shaped particles in parameters Pf and Z12. By experimental measurement, Pf values and Z12 of different samples are obtained. The experimental results show that, using the Z12 of oleic particles as the reference, the difference ΔZ12=12 can be used as the distinguishing threshold for spherical oleic acid particles and ellipsoidal riboflavin particles and long asbestos fibers particles. The ΔZ12 of riboflavin particles ranges from 12 to 41, and when ΔZ12 reaches 59, the particles can be considered as asbestos fiber particles. However, it’s hard to distinguish cubic NaCl particles and oleic acid particles because the values Z12 of each are very similar. Preliminary experiments show that Müller matrix element Z12 can be used to identify long particles, which can help to design morphology measurement instrument with polarization method.