Effect of cations on the magnetic and optical properties of Li2Pb2CuB4O10 has been explored. It is shown that Li2Pb2CuB4O10 is a paramagnetic material due to the absence of the exchange way between magnetic active units around copper ions, although a local magnetic moment about 1.59 mu(B) exists around Cu-O. Li2Pb2CuB4O10 exhibits a UV absorption edge of 356 nm which attributes to electronic transition between Cu, B and O. It reveals that the birefringence of Li2Pb2CuB4O10 is about 0.06 at 1064 nm which is mainly due to the arrangement of quasi-plane units of CuB4O10. The roles of lithium, copper, and lead are discussed and clarified in the magnetic and optical properties.