The most destructive wildfire experienced in Spain since 2004 occurred close to Valencia in summer 2012. A total of 48.500 ha were affected by two wildfires, which were mostly active during 29–30 June. The fresh smoke plume was detected at the Burjassot measurement station simultaneously to a severe dust episode. We propose an empirical method to evaluate the dust and smoke mixing and its impact on the microphysical and optical properties. For this, we combine direct-sun measurements with a Cimel CE-318 sun-photometer with an inversion methodology, and the Mie theory to derive the column-integrated size distribution, single scattering albedo (SSA) and asymmetry parameter (g). The mixing of dust and smoke greatly increased the aerosol load and modified the background aerosol properties. Mineral dust increased the aerosol optical depth (AOD) up to 1, while the smoke plume caused an extreme AOD peak of 8. The size distribution of the mixture was bimodal, with a fine and coarse modes dominated by the smoke particles and mineral dust, respectively. The SSA and g for the dust-smoke mixture show a marked sensitivity on the smoke mixing-ratio, mainly at longer wavelengths. Mineral dust and smoke share a similar SSA at 440 nm (~ 0.90), but with opposite spectral dependency. A small dust contribution to the total AOD substantially affects the SSA of the mixture, and also SSA at 1020 nm increases from 0.87 to 0.95. This leads to a different spectral behaviour of SSA that changes from positive (smoke plume) to negative (dust), depending on the dust and smoke mixing-ratio.