A PNP-pincer ligand provides a versatile ligation framework, which is highly useful in organometallic chemistry and catalytic chemistry. In this work, by a de novo strategy, a simple and efficient synthetic pathway, has been developed to prepare the new iminodibenzyl-based PNP pincer proligand imin-RPNP(Li or H) (R = isopropyl, phenyl). By employing salt metathesis or direct alkyl elimination, we successfully synthesized a series of iminodibenzyl-PNP rare-earth-metal (Ln = Sc, Y, Dy, Ho, Er, Tm, Lu) complexes and characterized them by NMR and X-ray diffraction analyses. Upon addition of a borate and triisobutylaluminum (TIBA), the rare-earth-metal complexes 2-Y, 2-Dy, 2-Ho, 2-Er, and 2-Tm bearing the imin-PhPNP ligand exhibited unexpectedly high 3,4-selectivity (up to 95%) for the polymerization of 1,3-dienes (isoprene and myrcene); in particular, the chosen yttrium complex 2-Y promoted the 1,3-diene polymerization in a living manner. A computational study suggested that the sterically congested configuration around the metal center imposed by the imin-RPNP ligand might be the main reason for this unusual selectivity.