The synthesis of novel block copolymers, namely poly(limonene-phthalate)-block-poly(pentadecalactone) and poly(limonene-phthalate)-block-poly(pentadecalactone) is here described. To achieve this synthesis, a bimetallic aluminum based complex (1) was used as catalyst in the combination of two distinct processes: the ring-opening polymerization (ROP) of macrolactones such as ω-pentadecalactone (PDL) and ω-6-hexadecenlactone (HDL) and the ring-opening copolymerization (ROCOP) of limonene oxide (LO) and phthalic anhydride (PA). The synthesis of di-block polyesters was performed in a one-pot procedure, where the semi-aromatic polyester block was firstly formed by ROCOP of LO and PA, followed by the polyethylene like portion produced by ROP of macrolactones (PDL or HDL). The obtained di-block semiaromatic polyesters were characterized by NMR and GPC. The structural organization was analyzed through XRD. Thermal properties were evaluated using differential thermal analysis (DSC) and thermogravimetric measurements (TGA) either in air or in nitrogen atmosphere.