Multi-layered plastic packaging consists of two or more types of polymers. It provides good mechanical properties with barriers against humidity, light and oxygen to ensure a longer shelf life of the products. However, due to a variety in packaging composition, it is challenging to perform mechanical or chemical recycling of these materials, which leads to landfill or incineration plant. Pyrolysis has been found as an alternative thermochemical recovery technology for mixed plastic waste and polymer materials that are challenging for recycling. Therefore, pyrolysis arises as a promising, environmentally friendly method of multi-layered plastic waste (MPW) treatment. Main products of pyrolysis are oil, gas and char, which can be further used to produce fuels, energy and chemicals. The composition characterization of sampled MPW was conducted using Fourier-transform infrared spectroscopy (FTIR) coupled with microscopy. The physicochemical properties of MPW were examined through proximate (moisture content, volatile matter, and ash content) and ultimate (elemental) analysis, as well as calorimetry. Non-isothermal thermogravimetric analysis was used to investigate the kinetics and mechanism of thermal degradation of MPW. The results obtained from this analysis were used to plan operational conditions (temperature, residence time, catalyst-to-polymer ratio) in a pilot-scale pyrolysis reactor. Experimental valorization of MPW was carried out in a pyrolytic laboratory reactor, both with and without catalyst usage, followed by analysis of the obtained products. Analytical methods employed for product analysis included Fourier-transform infrared spectroscopy, nuclear magnetic resonance (NMR), gas chromatography-mass spectrometry (GC-MS), and calorimetry. NMR analysis results indicated that the majority of the samples consisted of aliphatic hydrocarbons (alkanes and alkenes), followed by aromatic hydrocarbons, and in smaller proportions, aldehydes, vinyl groups, and -OH groups, consistent with FTIR results. GC-MS analysis of catalyst-treated samples confirmed the removal of oxygenated compounds that are undesirable in fuels. Calorimetric analysis demonstrated that pyrolytic products possessed relatively high higher heating values, ranging from 45.2 MJ kg-1 to 46.8 MJ kg-1. A techno-economic analysis of the conceptual pyrolysis plant solution for the selected real-world case study revealed the investment to be cost-effective, as evidenced by the obtained internal rate of return value, which was 15.54% after the analysis.