- William Smith (1769-1839), geologist
- William Smith (1728-1814), Representative for Maryland from 1789 to 1890
- William Smith (1751-1837), Representative for South Carolina from 1797 to 1798
- William Smith (1762-1840), Senator from South Carolina from 1815 to 1830
- William Smith, Representative for Virginia from 1821 to 1824
- William Smith, (1797-1887), Representative for Virginia from 1841 to 1860
See also
- Samuel William Smith, (1852-1931), Representative for Michigan from 1897 to 1914
- William Alden Smith, (1859-1932), Representative for Michigan from 1895 to 1906 and Senator from 1905 to 1918
- William Alexander Smith, (1825-1897), Premier of British Columbia), known as Amor De Cosmos
- William Alexander Smith, (1828-1888), Representative for North Carolina from 1873 to 1874
- William E. Smith, Governor of Wisconsin from 1878 to 1882
- William Ephraim Smith, (1829-1890), Representative for Georgia from 1875 to 1880
- William French Smith, United States Attorney General from 1981 to 1985
- William H. Smith, Governor of Alabama from 1868 to 1870
- William Jay Smith, (1823-1913), Representative for Tennessee from 1869 to 1870
- William Loughton Smith, (1758-1812), Representative for South Carolina from 1789 to 1798
- William Nathan Harrell Smith, (1812-1889), Representative for North Carolina from 1859 to 1860
- William Orlando Smith, (1859-1932), Representative for Pennsylvania from 1903 to 1906
- William Robert Smith, (1863-1924), Representative for Texas from 1903 to 1916
- William Russel Smith, (1815-1896), Representative for Alabama from 1851 to 1856
- William Stephens Smith, (1755-1816), Representative for New York from 1813 to 1816
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