The magnetic behavior and the transport behavior of La0.67-x Smx Sr0.33 MnO3 (x=0.00, 0.10, 0.20, 0.30,0.40, 0. 50 and 0. 60) systems were studied through measuring the M-T curves, electron spin resonance (ESR)curves and ρ-T curves. The samples exhibit a long-range ferromagnetic order when x = 0.00, 0.10, a cluster-spin glass state when x = 0. 20 and 0. 30, and an anti-ferromagnetic state at low temperatures when x = 0.40, 0. 50 and 0. 60. The samples of x = 0. 30 and 0. 40 show phase separation at temperatures above Tc. The transport behavior of the sample of x = 0. 60 becomes abnormal when the doping is high, and an insulator-metal transition occurs near Tcand then a metal-insulator transition occurs, which rarely appears in an ABO3 structure. It is concludedthat the magnetic and electric behavior changes of the systems depend on the extra magnetism and lattice distortion effect induced by Sm doping.