The formation of two distinct derivative structures of Ti2Ni-type, interstitial Pd3Cu3B and substitutive Pd5Cu5B2, has been elucidated in Pd-Cu-B alloys from analysis of X-ray single crystal and powder diffraction data and supported by SEM. The metal atom arrangement in the new boride Pd3Cu3B (space group , W3Fe3C-type structure, a=1.1136(3) nm) follows the pattern of atom distribution in the CdNi-type structure. Pd5Cu5B2 (space group , a=1.05273(5) nm) exhibits a non-centrosymmetric substitutive derivative of the Ti2Ni-type structure. The reduction of symmetry on passing from Ti2Ni-type structure to Pd5Cu5B2 corresponds to the loss of the axis delivered by an ordered occupation of the Ni position (32e) by dissimilar atoms, Cu and B. In both structures, the boron atom has only contact to Pd forming [BPd6] octahedra in Pd3Cu3B and [BPd6] trigonal prisms in Pd5Cu5B2. Neither a perceptible homogeneity range nor mutual solid solubility was observed for two compounds at 600 C, while in as cast conditions Pd5Cu5B2 exhibits extended homogeneity range formed by a partial substitution of Cu atoms (in 24f) by Pd (Pd5+xCu5-xB2, 0x1). Electrical resistivity measurements performed on Pd3Cu3B as well as on Pd-poor and Pd-rich termini of Pd5+xCu5-xB2 annealed at 600 C and in as cast conditions respectively demonstrated the absence of any phase transitions for this compounds in the temperature region from 0.3 K to 300 K.