The wetting and evaporation behavior of droplets of aqueous solutions of mixtures of poly(diallyldimethylammonium chloride) solution, PDADMAC, with two different anionic surfactants, sodium laureth sulfate, SLES, and sodium N-lauroyl N-methyl taurate, SLMT, were studied in terms of the changes of the contact angle θ and contact length L of sessile droplets of the mixtures on silicon wafers at a temperature of 25 °C and different relative humidities in the range of 30–90%. The advancing contact angle θa was found to depend on the surfactant concentration, independent of the relative humidity, with the mixtures containing SLES presenting improved wetting behaviors. Furthermore, a constant droplet contact angle was not observed during evaporation due to pinning of the droplet at the coffee-ring that was formed. The kinetics for the first evaporation stage of the mixture were independent of the relative humidity, with the evaporation behavior being well described in terms of the universal law for evaporation.