The p-tert-butyl calix[4]arene symmetrical sulfide derivatives (3a and 3b) were successfully synthesized using p-tert-butyl calix[4]arene as the raw material and were characterized by FT-IR. The effects of pH value, temperature, and contact time on the U(VI) extraction with compounds 3a and 3b from aqueous solution were systematically investigated. The results showed that the optimum pH value for uranium extraction was 4.0 and the extraction equilibration time was 90 min. It is also found that the pseudo-second-order kinetic model (R2 > 0.999) was better fitted to the extraction process. The thermodynamic parameters of the enthalpy (ΔHθ) were all negative, indicating that the extraction reaction were exothermic reaction.