This work presents the first use of Cofalit® (vitrified asbestos-containing waste) as a solid filler in pilot-scale thermocline thermal energy storage (TES). The thermocline size is 4 m³ connected to the MicroSol-R installation at the PROMES research facility in Odeillo, France. The study compares the thermal performance of the thermocline filled with Cofalit® to the reference case of alumina spheres for typical charge and discharge operations. It evaluates the actual thermal behavior of thermocline considering three leading performance indicators: process duration, thermocline thickness, and process efficiency. The investigation shows a 22% shorter charge duration in Cofalit® compared to alumina and 16% shorter discharge duration. Cofalit® exhibits about 16% lower thermocline thickness during both charge and discharge compared to alumina. The charge efficiency is slightly better in Cofalit® than alumina with an efficiency of 82% and 78%, respectively. Also, Cofalit® has a better discharge efficiency, 90% with respect to 84% for alumina. These results confim a good thermal performance of Cofalit® as filler material in thermocline TES. Considering the cost-saving and positive environmental impact of using Cofalit® as well as the good thermal performance of the thermocline filled with it, Cofalit® appears a very good filler material in TES. The obtained temperatures from radial positions indicate no significant variation during charge and discharge, and this confirms the one-dimensional thermal behavior of this setup. A parametric analysis is performed using a 1D continuous solid (C-S) model to investigate the influence of particle diameter, porosity, thermal conductivity, and volumetric heat capacity on the thermal performance of the thermocline. The analysis confirms the experimental findings, and it indicates that about a 10.9% longer process duration is associated with a 10% larger volumetric heat capacity and less affected with other parameters. Thermocline thickness is mainly affected by the diameter as well as the volumetric heat capacity of the solid filler; it grows 2.2% for each 10% diameter increase and around 3.23% for doubling the volumetric heat capacity. Charge efficiency demonstrates independency from evaluated properties. While discharge efficiency increases sharply at a tiny particle diameter before an optimum diameter value is reached, then it starts to decrease by 1.4% to each 10% bigger diameter.