Abstract: The PbO–BaO–B2O3–SiO2 system is studied using solid-state synthesis and melt crystallization methods and attempts are made to obtain samples of the maleevite (BaB2Si2O8)—lead maleevite (PbB2Si2O8) series. Due to the strong tendency of Pb-containing borosilicate materials to form glass, a lead-enriched analogue of maleevite is not obtained. In the study, a new lead borate Pb2B6O11 (sp. gr. P–1, a = 6.582(1) Å, b = 6.593(1) Å, c = 11.310(2) Å, α = 98.29(1)°, β = 90.65(1)°, γ = 119.10(2)°, V = 422.4(1) Å3) and a series of solid solutions (Ba1 –xPbx)3B6Si2O16 (x = 0.2, 0.4, 0.6) are synthesized and characterized for the first time. The layered compound Pb2B6O11 has a new structural type, while the solid solution (Ba1 – xPbx)3B6Si2O16 is a structural analogue of the previously known Ba3B6Si2O16.