A　new　compound,　Li(4)WaB(2)O(6),　has　been　synthesized　by　solid-state　reaction　and　its　structure　has　been　determined　from　powder　X-ray　diffraction　data　by　direct　methods.　The　refinement　was　carried　out　using　the　Rietveld　methods　and　the　final　refinement　converged　with　R-p　=　10.4%　R-wp　=　14.2%,　R-exp　=　4.97%.　This　compound　belongs　to　the　orthorhombic　space　group　Pnnm,　with　lattice　parameters　a　9.24036(9)　Angstrom,　b　=　8.09482(7)　Angstrom,　and　c　=　3.48162(4)　Angstrom.　Fundamental　building　units　are　isolated　[BO3](3-)　anionic　groups,　which　are　all　parallel　to　the　a-b　plane　stacked　along　the　c-axis.　The　Ca　atoms　are　six-coordinated　by　the　O　atoms　to　form　octahedral　coordination　polyhedra,　which　are　joined　together　through　edges　along　the　c-axis,　forming　infinitely　long　three-dimensional　chains.　The　Li　atoms　have　a　four-fold　and　a　five-fold　coordination　with　O　atoms　that　lead　to　complex　Li-O-Li　chains　that　also　extend　along　the　c-axis.　The　infrared　spectrum　of　Li4CaB2O6　was　also　studied,　which　is　consistent　with　the　crystallographic　study.　(C)　2003　Elsevier　Inc.　All　rights　reserved.