The dipyrromethene (DPM) ligand is the key to isolation of monomeric Zn hydride complexes with tricoordinate zinc centers. A range of RDPM ligands with various substituents in the pole position (1,9‐positions) were prepared: R = tBu, adamantyl (Ad), mesityl (Mes), 2,6‐diisopropylphenyl (DIPP), 2,4,6‐triphenylphenyl (Mes*), or 9‐anthracenyl (Anth). Reaction of the ligands with Et2Zn gave a series of (RDPM)ZnEt complexes, which were converted with I2 to the corresponding (RDPM)ZnI compounds. The latter reacted by salt metathesis with KN(iPr)HBH3 to the series of Zn hydride complexes (RDPM)ZnH. For ligands with the larger Mes* and Anth substituents, (RDPM)ZnEt was converted to (RDPM)ZnOSiPh3, which after reaction with PhSiH3 gave the hydrides. While Zn hydride complexes with R = tBu or Ad are dimeric, all complexes with aryl‐substituents are monomeric. The aryl groups span a cavity around the metal, blocking dimerization and causing a high‐field shift of the 1H NMR signals due to the ASIS effect. Attempted abstraction of the hydride with B(C6F5)3 led to cleavage of the B‐C6F5 bond.