In this work, we investigated the potential use of high-consistency silicone rubber (SR), which is a synthetic solid material used in numerous industrial applications, to produce a range of liquid alkoxysiloxane derivatives R(OSiMe2)(x)OR, with x = 1 (P-1), 2 (P-2), 3 (P-3), and 4 (P-4). We describe a simple and convenient solvothermal alcoholysis method for the chemical recycling of post-consumer SR in the presence of fatty alcohols under catalyst-free or catalytic conditions. This process proceeds easily both without and with a catalyst. Alkali-metal aryloxides supported by a methylsalicylato ligand (MesalO) gave the highest conversions of SR to products P-1-P-4. Magnesium and zinc aryloxides enabled efficient conversions of products P-2-P-4 to P-1. Binary metal catalysts of general formula [M2M'(2)(MesalO)(6)] (M = Mg or Zn; M' = Li, Na, or K), which had a combination of the catalytic properties shown by alkali-metal aryloxides and magnesium/zinc aryloxides, were produced and used to synthesize P-1-P-4. The results show that magnesium-sodium/potassium aryloxides had the best catalytic activities. Their use led to the formation of two dominant products, namely, P-1 and P-2, with conversion yields of 79 and 17%, respectively. Particular emphasis is placed on the operating conditions and high activity of the catalyst used. Key factors that affect the catalytic activity and reaction mechanism are also highlighted.