The aim of the present study is to determine four anionic alkyl sulfate (AS) surfactants with different alkyl chains, namely, C8, C10, C12, and C14, in wastewater by CE with capacitively coupled contactless conductivity detection (CE‐C4D). The conditions effective for the separation of the four AS surfactants were systematically optimized and found to be in a Tris‐His (50 mM/20 mM) BGE solution at a pH of 8.95, using a separation voltage of +15 kV, hydrodynamic injection by siphoning using a 20 cm injection height and an injection time of 20 s. The LODs for C8, C10, C12, and C14 were 2.58, 2.30, 2.08, and 3.16 mg/L, respectively. The conditions used to achieve the simultaneous adsorption and preconcentration of the AS surfactants using Al2O3 beads were pH of 3 and 0.1 mM NaCl. The adsorption efficiencies were found to be 45.6, 50.8, 81.7, and 99.9%, while the desorption efficiencies reached 66.1, 70.4, 83.9, and 100.0% for C8, C10, C12, and C14, respectively. The concentrations of the AS surfactants in wastewater samples were quantified by CE‐C4D after preconcentration by simultaneous adsorption using Al2O3 beads. The results obtained from the proposed method were consistent with those obtained by HPLC‐MS/MS, with a deviation of less than 15%. Our results indicate that the CE‐C4D performed after preconcentration by an adsorption technique using Al2O3 beads is a new, inexpensive, and suitable method for quantifying AS surfactants in wastewater samples.