Webster was born in Charlotte, New York in 1851 and married Annie Moffett, Mark Twain's niece, in 1875.

[1] The following year, Annie gave birth to a daughter, Alice Jane Chandler Webster.

In 1881, Twain hired Webster to oversee the development of Twain's investments for the Kaolatype process for making engraved printing plates.

[2] When Twain decided to start his own publishing company in 1884, he hired Webster to head the company and named it after him, promoting him to full partner in March 1885.

[3] Webster's son, Samuel Charles Webster, published the book Mark Twain, Business Man in 1946 to rehabilitate his father's reputation.