Radar observation and signature identification of human motions have a variety of applications in social security and rescue operations. Both simulation and real radar experiment are conducted to investigate the polarimetric micro-Doppler signatures (MDSs) of a pedestrian. In the simulation, the motion-captured dataset developed by Carnegie Mellon University motion graphic laboratory is first used, then both Feldberechnung bei Korpern mit beliebiger Oberflache (FEKO) and MATLAB are used to calculate the radar scattering of pedestrian’ arms, based on which, horizontal-horizontal (HH) and horizontal-vertical (HV) polarimetric MDSs are analysed. Simulation results clearly show that in the time–frequency diagram, HH micro-Doppler (m-D) of arms is rising, whereas HV m-D is falling, which is verified by practical Ka-band radar experiment on a pedestrian. The work shows that by using polarimetric radar the m-D signature of human motion can be much well detected and identified which can be further explored for classification of different people.