The high-specific activity 99Mo accelerator-based production, via the (α,n) reaction on 96Zr-enriched target, has been investigated in the present work. The excitation function measurement has been performed in the energy range 8–34 MeV at the ARRONAX facility, using the well-known stacked foils technique on natural zirconium as target. A general good agreement in the cross section trend has been observed, once compared to former measurements. A different (i.e. higher) peak value and a shift of about 2 MeV towards larger energies have however been found. Assuming a fully enriched 96Zr target irradiated by an α-beam at suitable energy (E = 25 MeV), the 99Mo production yield has thus been estimated. At last the alternative production routes, based on the 96Zr(α,n)99Mo and 100Mo(p,x)99Mo/99mTc reactions, are compared