Edward Charles Williams was the son of painter Edward ‘Moonlight’ Williams, a nephew of James Ward. He had five brothers, all of whom also became landscape painters: Henry John Boddington; George Augustus Williams, Alfred Walter Williams, Sidney Richard Percy and Arthur Gilbert. (Several altered their surnames to distinguish themselves from their painter brothers.) Williams probably trained in his father's studio. He exhibited between 1839 and 1865 at the Royal Academy, the British Institution, the Society of Artists and other locations. In 1861 he appeared at the Court for Relief of Insolvent Debtors, which may account for his frequent changes of address. He settled in Hammersmith in c.1853, where he remained for the rest of his career.
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