Christopher Pike, he was featured in that two part series
Spock was never the captain in the series, but he was the first officer and cheif science officer aboard the U.S.S. Enterprise.
Chronologically, Captain Jonathan Archer was the captain of the first starship Enterprise in the prequel series Enterprise (2001-2005) However, Captain James T. Kirk was the first captain to appear in the franchise, on the original series (TOS) from 1966-1969. An earlier captain of the Enterprise NCC-1701 was Captain Christopher Pike, who appeared in the first Star Trek pilot filmed in 1964. Star Trek pilot (added to TOS as "The Cage") - Christopher Pike (Jeffrey Hunter) Star Trek the original series - James T. Kirk (William Shatner) Star Trek / Enterprise - Jonathan Archer (Scott Bakula)
In the Original Star Trek Series Spok was Second in Command of the Enterprise NCC-1701. In Star Trek The Next Generation Commander Willaim T. Riker is the Second in Command/First Officer of the USS Enterprise NCC-1701-D (Galaxy Class Starship used in the series)
The fictional captain of the starship enterprise, from Star Trek (the original series, first 4 films, and 2 new reboot films).
Captain Jonathan Archer (Scott Bakula)
Star Trek TOS (the original series) : James T. KirkStar Trek TNG (The Next Generation) : Jean-Luc PicardStar Trek VOY (Voyager, not Enterprise) : Kathryn JanewayStar Trek ENT (series Enterprise) : Jonathan Archer---Star Trek captains on all 5 live-action TV series :James T Kirk - Star Trek (the original series 1966-1969)Jean-Luc Picard - Star Trek: The Next Generation (1987-1994)Benjamin Sisko - Star Trek: Deep Space 9 (1993-1999)Kathryn Janeway - Star Trek: Voyager (1995-2001)Jonathan Archer - Star Trek: Enterprise (nee Enterprise 2001-2005)
In the original series (Gene Roddenberry, 1966), the captain of the Enterprise was James Tiberius Kirk, and the first officer Spock. In Star Trek: The Next Generation (Gene Roddenberry, 1987), the captain is Jean-Luc Piccard, and the first officer William Thomas Riker. In the chronologically earlier series, Star Trek: Enterprise (Rick Berman, Brannon Braga, 2001), the captain of the Enterprise is Jonathan Archer, and the first officer T'Pol.
Scott Bakula played Captain Jonathan Archer in Star Trek: Enterprise.
The first season of Star Trek was broadcast 1966-1967 and starred William Shatner as Captain Kirk, exploring the galaxy on the Starship Enterprise.
United Star Ship Enterpise
NCC 1701
The captain of the starship Enterpize was James T Kirk. Many people can get confused to know if its James T Kirk or Alan Shepard because Alan was the first US astronaut but the captain was definitely James T Kirk.