The properties of GaAsSbN and GaAsSb layers grown by liquid-phase epitaxy on n-GaAs substrates were investigated in a comparative plan with a view of their possible application in multi-junction solar cells. To avoid non-uniformity effects in the composition of these compounds with two or three different group-V volatile elements, the crystallization was carried out from finite melt with a thickness of 0.5 mm at low (<560 °C) temperatures. X-ray microanalysis and X-ray diffraction were used to determine the composition, lattice mismatch, and crystalline quality of the epitaxial layers. The morphology and surface roughness were examined by atomic force microscopy. Surface photovoltage (SPV) spectroscopy at room temperature was applied to study the optical absorption properties and the photocarrier transport in the samples. The long-wavelength photosensitivity of the GaAsSbN and GaAsSb layers, determined from their SPV spectra, is extended down to 1.2 eV. Although GaAsSb has a slightly larger lattice mismatch with the GaAs substrate compared to GaAsSbN, it presents a higher photoresponse, since, in GaAsSbN, the incorporation of N induces additional recombination centres. Therefore, GaAsSb could be an alternative to GaAsSbN for solar cell applications.