By both experimental measurements and theoretical calculations, we investigated the magnetic and electronic properties of Li2Cu(WO4)(2) as a tungstate-bridged quasi-one-dimensional (1D) copper spin-(1/2) chain system. Interestingly, magnetic susceptibility chi(T) and specific heat measurements show that the system undergoes a three-dimensional antiferromagnetic (AF)-like ordering at T-N approximate to 3.7 K, below a broad chi(T) maximum at similar to 8.9 K indicating a low-dimensional short-range AF spin correlation. Bonner Fisher model fitting of chi(T) leads to an AF intrachain exchange constant of J/k(B) = 15.8 +/- 0.1 K, and mean-field theory estimation gives an interchain coupling constant of J(sic)/k(B) = 1.6 K, which supports the quasi-1D nature of this spin system. Theoretical evaluation of exchange coupling constants within the generalized gradient approximation (GGA) plus on-site Coulomb interaction (U) shows that the dominant AF exchange interaction is of similar to 13.9 K along the a-axis with weak interchain coupling, in agreement with the experimental result of a quasi-1D spin-(1/2) chain system. The GGA+U calculations also predict that Li2Cu(WO4)(2) is a charge transfer-type AF semiconductor with a direct band gap of 1.5 eV.