The reaction of Na10[α-SiW9O34] with tetravalent metallic cations such as 4f ((NH4)2Ce(NO3)6), 5d (HfCl4), or 5f (UCl4 and Th(NO3)4) in a pH 4.7 sodium acetate buffer solution leads to the formation of four sandwich-type polyoxometalates [Ce4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (1), [U4(μ(3)-O)2(SiW9O34)2(CH3COO)2](10-) (2), [Th3(μ(3)-O)(μ(2)-OH)3(SiW9O34)2](13-) (3), and [Hf3(μ(2)-OH)3(SiW9O34)2](11-) (4). All four compounds consist of a polynuclear cluster fragment stabilized by two [α-SiW9O34](10-) polyanions. Compounds 1 and 2 are isostructural with a tetranuclear core (Ce4, U4), while compound 3 presents a trinuclear Th3 core bearing a μ(3)-O-centered bridge. It is an unprecedented configuration in the case of the thorium(IV) cluster. Compound 4 also possesses a trinuclear Hf3 core but with the absence of the μ(3)-O bridge. The molecules have been characterized by single-crystal X-ray diffraction, (183)W and (29)Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis.