Synthesis of the peripherally substituted (phthalocyaninato)metal derivatives (NO2)4PcM (M α Ni, Co, Cu; NO2groups are in 1,8,15,22- or 2,9,16,23-positions) is described, and their X-ray powder diffraction patterns, solubilities, electronic and infrared spectra, and thermal stability are reported. The complexes exhibit isomorphism and polymorphism, and they are more soluble than the corresponding MPcs. Their thermal stability increases in the series Co < Ni < Cu, being at the same time greater for the 2,9,16,23-tetranitro- than for the 1,8,15,22-tetranitro derivatives.