Electrophilic substitution of acylmethanes (methyl ketones), RCOCH₃ (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl₃ (Ar = 1-C₁₀H₇, Np, A; 2,4,6-Me₃C₆H₂, Mes, B; 4-MeOC₆H₄, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH₂)ArTeCl₂. Reduction of the dichlorides, gives tellurides, (i-PrCOCH₂)ArTe, 1A–1C, which give the corresponding dihalides, (i-PrCOCH₂)ArTeX₂ (X = Cl, 1Aa–1Ca; Br, 1Ab–1Cb; I, 1Ac–1Cc) when reacted in situ with SO₂Cl₂, Br₂ or I₂. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar₂Te₂ except in the case of (i-PrCOCH₂)MesTe (1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate ¹H and ¹³C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te–C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one ¹²⁵Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1Ca and 1Cc which are indicative of the presence of intramolecular Te⋯O secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te–C(mesityl) bond axis. Intermolecular C–H⋯O H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.