We report synthesis and magnetic properties of quasi-one-dimensional spin-12 Heisenberg antiferromagnetic chain compound BaNa2Cu(VO4)2. This orthovanadate has a centrosymmetric crystal structure, C2/c, where the magnetic Cu2+ ions form spin chains. These chains are arranged in layers, with the chain direction changing by 62∘ between the two successive layers. Alternatively, the spin lattice can be viewed as anisotropic triangular layers upon taking the interchain interactions into consideration. Despite this potential structural complexity, temperature-dependent magnetic susceptibility, heat capacity, electron spin resonance intensity, and nuclear magnetic resonance (NMR) shift agree well with the uniform spin-1/2 Heisenberg chain model with an intrachain coupling of J/kB≃5.6 K. The saturation field obtained from the magnetic isotherm measurement consistently reproduces the value of J/kB. Further, the V51 NMR spin-lattice relaxation rate mimics the one-dimensional character in the intermediate temperature range, whereas magnetic long-range order sets in below TN≃0.25 K. The effective interchain coupling is estimated to be J⊥/kB≃0.1 K. The theoretical estimation of exchange couplings using band-structure calculations reciprocate our experimental findings and unambiguously establish the one-dimensional character of the compound. Finally, the spin lattice of BaNa2Cu(VO4)2 is compared with the chemically similar but not isostructural compound BaAg2Cu(VO4)2. © 2021 American Physical Society.