Preparation, analytical characterization, and crystal structures of N,N′-bis(thiophen-2-ylmethyl)ethane-1,2-diaminium hydrochloride (1) and of its gold derivative, N,N′-bis(thiophen-2-ylmethyl)ethane-1,2-diaminium tetrachloroaurate(III) (2) are reported. Compound (1) was obtained by reduction of the Schiff base N,N′-bis(thiophen-2-ylmethyl)ethane-1,2-diamine followed by HCl solution addition, whereas compound (2) was prepared reacting (1) with K[AuCl4] in aqueous solution. Compound (1) crystallizes in the orthorhombic system with space group Iba2 and cell parameters a = 29.856(1), b = 5.1372(2), and c = 10.1635(4) Å. Crystals of (2) belong to the monoclinic system with space group P21/c and cell parameters a = 11.0829(1), b = 9.5852(1), c = 11.6054(2) Å, and β = 75.49(1)°. Both structures contain diprotonated organic moieties, counterbalanced by hydrogen-bonded Cl−, or [AuCl4]− ions, in compounds (1) and (2), respectively.