Synthesis and structure of new (Bi, La)3MSb2O 11 phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi 3CrSb2O11, Bi2LaCrSb 2O11, Bi2LaMnSb2O11 and Bi2LaFeSb2O11 adopt KSbO3-type structure (space group, Pn3). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O6 octahedral network and other two are the identical networks having Bi6O4 composition. The magnetic measurements on Bi2LaCrSb2O11 and Bi2LaMnSb 2O11 show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr+3 and Mn +3. The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of ∼ 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light. © Indian Academy of Sciences.