In this contribution, we describe the use of graphene as an efficient catalyst support and the role it plays in increasing the Lewis acidity of the supportedm etal complexes.B yadensity functional theorys tudy,w eshowt hat the [La(N(SiMe 3) 2) 3 ]c omplex can be easily grafted on graphene-OHa nd-COOHf unctionalized surfaces. Twos table mono-grafted compounds, (gO)-[La(N(SiMe 3) 2) 2 ]a nd (gOO)-[La(N(SiMe 3) 2) 2 ], are formed, behaving as stronger Lewis acids than the previously reported silica grafted analogues. To study the role of the graphene support in catalysis, we also computed the catalytic activity of the alkylated (gO)-[La(CH 3) 2 ]a nd (gOO)-[La(CH 3) 2 ]c omplexes in the ethylene and 1,3-butadiene homo-and co-polymerizationr eactions. Both compounds are efficient catalysts fort he homo-polymerization of the ethylene and 1,3-butadiene. For the 1,3butadiene homo-polymerization, the stereoselectivity outcome of the reactiond iffers according to the grafting site. The resultsc omputed for the co-polymerization reaction, finally,s how that the high stability of the allylic products leads to the formationo fb lock copolymers.