Abstract Eleven calixarene rare earth complexes were prepared by alcohol–phenol exchange reaction of rare earth isopropoxides with calixarenes in toluene. These rare earth calixarene complexes combined with Al(iBu) 3 were found for the first time to be effective homogeneous catalysts to polymerize ethylene. The effects of Al/Nd molar ratio and reaction temperature on the polymerization were investigated. The catalytic activity of calix arene neodymium system is 39.5 kg PE/mol Nd h giving polyethylene with viscosity average molecular weight of 93.1×10 4 under the following conditions: [Nd]=1×10 −3 mol/l −1, Al/Nd=15, T=80°C, time=0.5 h, ethylene pressure =1.2 MPa. AlBu 2H, AlEt 3 can be used instead of Al(iBu) 3 to form effective catalyst with calix arene neodymium for ethylene polymerization.