Pike first joined the fraternal Independent Order of Odd Fellows in 1840. He next joined a Masonic Lodge, where he became extremely active in the affairs of the organization. In 1859 he was elected Sovereign Grand Commander of the Scottish Rite's Southern Jurisdiction. He remained Sovereign Grand Commander for the remainder of his life (a total of thirty-two years), devoting a large amount of his time to developing the rituals of the order. Notably, he published a book called Morals and Dogma of the Ancient and Accepted Scottish Rite of Freemasonry in 1871, of which there were several subsequent editions. This helped the order grow during the nineteenth century.

 

In America, Pike is still considered an eminent and influential Freemason, primarily in the Scottish Rite Southern Jurisdiction.

 

Settling in Arkansas in 1833, Pike taught in a school and wrote a series of articles for the Little Rock Arkansas Advocate under the pen name of "Casca." The articles were popular enough that he was asked to join the newspaper's staff. Under Pike's administration, the Advocate promoted the viewpoint of the Whig Party in a politically volatile and divided Arkansas in December 1832. After marrying Mary Ann Hamilton in 1834, he purchased the newspaper.

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He was the first reporter for the Arkansas Supreme Court. He wrote a book (published anonymously), titled The Arkansas Form Book, which was a guidebook for lawyers. Pike began to study law and was admitted to the bar in 1837, selling the Advocate the same year.

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He also made several contacts among the Native American tribes in the area. He specialized in claims on behalf of Native Americans against the federal government. In 1852 he represented Creek Nation before the Supreme Court in a claim regarding ceded tribal land. In 1854 he advocated for the Choctaw and Chickasaw, although compensation later awarded to the tribes in 1856 and 1857 was insufficient. These relationships were to influence the course of his Civil War service.

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Additionally, Pike wrote on several legal subjects. He also continued writing poetry, a hobby he had begun in his youth in Massachusetts. His poems were highly regarded in his day, but are now mostly forgotten. Several volumes of his works were privately published posthumously by his daughter. In 1859, he received an honorary Master of Arts degree from Harvard.