A surfactant-induced autophobic effect has been observed to initiate an intense depinning behavior at the initial stage of evaporation in both pure water and nanofluid sessile droplets. The cationic surfactant adsorbing to the negatively charged silicon wafer makes the solid surface more hydrophobic. The autophobing-induced depinning behavior, leading to an enlarged contact angle and a shortened base diameter, takes place only when the surfactant concentration is below its critical micelle concentration (cmc). The initial spreading degree right before the droplet retraction, the retracting velocity of the contact line, and the duration of the initial droplet retraction are shown to depend negatively on the surfactant concentration below the cmc. An unexpected enhancement in the initial depinning has been found in the nanofluid droplets, possibly resulting from the hydrophilic interplay between the graphite nanoparticle deposition and the surfactant molecules. Such promotion of the initial depinning due to the nanoparticle deposition makes the droplet retract even at a surfactant concentration higher than the cmc (1.5 cmc). The resulting deposition formed in the presence of the depinning behavior has great enhancement for coffee-ring formation as compared to the one free of surfactant, implying that the formation of a coffee ring does not require the pinning of the contact line during the entire drying process.