We show that the replacement of Mn with Cu, without any structure change, strongly affects the transport and magnetic behaviors in La2/3Ca1/3 Mn1-xCuxO 3 - δ (x?0.3). Doping largely shifts the insulator-metal transition towards the low-temperature regime and causes substantial enhancements in both resistance and magnetoresistance near the transition for doping range of x? 15%, and further doping to x≥ 20% shows insulating behavior. For 15% doping, the sample shows large magnetoresistances (∼104%) over the whole low temperature range. Magnetization measurement at helium temperature reveals that samples for x? 10% and ≥ 20% basically show ferromagnetic (FM) and antiferromagnetic (AF) behaviors, respectively, while the 15% Cu doped sample undergoes a metamagnetic transition from AF state to FM state on increasing field. We argue that doping introduces the AF insulating phase into the system, causing unusual transport and magnetic behaviors.