Di-n-hexyl sulfide (DHS) has been widely utilized as a practical extractant for palladium for many years. Despite its high selectivity for Pd(II) extraction, two problems have been identified in industrial operations: slow Pd(II) extraction and low durability. In order to address these issues, we have introduced sulfides that exhibit a high affinity for Pd(II) into amphiphilic N,N-disubstituted amides utilized for the extraction of metals from highly concentrated acid solutions. Several derivatives of sulfide-containing monoamide and diamide compounds were synthesized and utilized for the extraction of Pd(II) from HCl solutions. The extraction of Pd(II) by these compounds was found to be faster than that of DHS. The Pd(II) complexes with these compounds were analyzed using XAFS, singly crystal XRD, and FT-IR measurements, indicating that the amide oxygen atom does not directly coordinate with the Pd(II) but the sulfur atom does. Slope analyses of the distribution ratios of Pd(II) suggest that the stoichiometry of the Pd complexes extracted in the organic phase was 1:2 for Pd(II):amide with a sulfide and 1:1 for Pd(II):amide with two sulfides. Among the compounds, thiodiglycolamide (TDGA), a sulfide-containing diamide, was identified as the most suitable for practical synthesis; therefore, we investigated its application characteristics for practical use. With regard to the durability of the compounds, TDGA demonstrated higher oxidation resistance to strongly acidic aqueous solutions. Furthermore, the Pd(II) extracted with TDGA can be readily back-extracted using an aqueous ammonia solution, and the Pd(II) loading capacity is sufficient. Thus, TDGA can overcome the shortcomings of DHS, and is therefore commercially available and has been adopted in industrial processes.