By application of flux growth methods in combination with redox reactions, single crystals of BaAg(2)Cu[VO(4)](2) can be synthesized. A new structure type (triclinic, P1, Z = 2, a = 5.448(2) Å, b = 5.632(3) Å, c = 14.393(6) Å, α = 94.038(9)°, β = 90.347(6)°, and γ = 118.195(5)°) has been found and will be described here. Structure-properties relationships have been investigated by spectroscopic methods (IR, UV-vis-NIR, ESR) and the electronic structure will be discussed within the angular-overlap model (AOM) for Cu(2+). Furthermore, we present the magnetization and specific heat data for BaAg(2)Cu[VO(4)](2) representing a Heisenberg spin system with exclusive super-super exchange (SSE) on a frustrated magnetic triangular lattice. Considerable antiferromagnetic (AFM) low-dimensional interaction is evident, and ferromagnetic-like long-range order sets in at ≈0.7 K.