In situ propene polymerization was observed using CP MAS (cross polarization with magic angle spinning) C-13 NMR spectroscopy under the conditions of continuously flowing propene through a supported Ziegler catalyst treated with triethylaluminium. The signals at 44, 26, and 22 ppm attributed to the CH2, CH, and CH3 groups of polypropene, respectively, were found to appear upon exposure to the propene flow (0.1 L/min). An increase in intensities of these lines was observed for 30 min, then they remained approximately constant. The cross-polarization parameters of nascent polypropene, measured using standard techniques, were close to those of typical crystalline polypropene. The technique has a great potential as an effective tool for the investigation of the polypropene formation on the Ziegler catalyst.