A systematic study of structural and electrical properties of GaSb and AlGaSb grown on GaAs by metalorganic chemical vapor deposition is reported. In general, the results obtained from surface morphologies, X-ray linewidths and Hall properties are consistent with each other and indicate that the optimal growth conditions for GaSb are at 525°C around V/III = 1. A highest hole mobility of 652 cm2/V · s at RT (3208 cm2/V · s at 77 K) and a lowest concentration of 2.8 × 1016 cm-3 (1.2 × 1015 cm-3 at 77 K) were obtained for GaSb grown under this optimal condition. Compared to the GaSb growth, a smaller V/III ratio is needed for the AlGaSb growth to protect the surface morphology. When Al was incorporated into GaSb growth, mobility decreased and carrier concentration increased sharply. The AlGaSb grown at 600°C had a background concentration about one order of magnitude lower than the AlGaSb grown at 680°C. Room-temperature current-voltage characteristics of GaSb/AlxGa1-xSb/GaSb show a rectifying feature when Al composition x is higher than 0.3, suggesting a valence-band discontinuity at the AlGaSb/GaSb interface. A leakage current much higher than the value predicted by the thermionic emission theory is observed at 77 K, presumably due to a large number of dislocations generated by the huge lattice mismatch between GaSb and GaAs.