The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C-5-C-32 yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, alpha-olefins and alpha,omega-dienes were detected. Increasing the decalin/plastic ratio led to enhanced alpha-olefin and n-paraffins yields, but the increase was more significant in the case of alpha-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical beta-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.