A series of Cu-substituted goethites, single and co-substituted with Cr, Zn, Cd and/or Pb was prepared, having molar ratios equal to 2.00, 3.33 and 5.00 mol%. All the samples contained only goethite, except Cu-, (Cu,Zn)- and (Cu,Pb)-samples synthesized at 5.00 mol% where hematite was also formed. The presence of Cr/Cd suppressed the hematite-forming effects of Cu. The general sequence of metal entry into the single-metal-substituted goethites was Zn = Cr > Cd > Cu > Pb and in di- (5.00 mol%) and tri- (3.33 mol%) metal-substituted goethites was Cu > Zn > Cd > Cr ≫ Pb. Cu incorporation increased all the unit-cell parameters in single-metal-substituted goethite, and these parameters increased in combination with other metals as follows: Cd > Zn > Cr > Pb in the multi-metal-substituted goethites. The Cu-substituted goethite dissolved faster than pure goethite. Co substitutions of Cr/Pb reduced the dissolution rate (kFe), while substitutions of Cd/Zn increased kFe.