We have performed neutron powder diffraction (NPD) experiments on polycrystalline powders with nominal compositions (Ca0.5La0.5)(Ba1.25La0.75)Cu3O7- δ , (Ca0.6La0.4)(Ba1.15La0.85)Cu3O7-δ and (Ca0.8La0.2)(Ba0.95La1.05)Cu3O7-δ . The diffraction patterns, analysed by the Rietveld method, show that all samples consist mainly of a tetragonal Y-123 type phase. Unit cell parameters a and c shorten as the calcium content increases: a = 3.8660(2), 3.8634(3), and 3.8624(5) Å; c = 11.6325(11), 11.6143(14), and 11.5822(20) Å for x-values 0.5, 0.6, and 0.8, respectively. For the x = 0.6 and 0.8 samples the Rietveld refinement of calcium occupancies and EDX analysis suggest that the actual composition is closer to x ≈ 0.5. However, since the lattice parameters do change, it is also suggested that at these higher doping levels calcium does enter the Y- site to a larger extent than for the x = 0.5 composition. This is also in accordance with previously reported values for the Tc, which decreases slighty as x changes from 0.5 to 0.6 and has a pronounced change from 80 K to 73 K for x = 0.6 and 0.8, respectively.