Phillips departed the Gladiators by mutual consent back in September.
He led Matlock and previous employers Buxton to the Northern Premier League play-offs.
He also enjoyed considerable success during three seasons at Ashton United, whom he also helped to the play-offs.
Phillips will be joined by Kayde Coppin, who was previously his assistant at Matlock.
Coppin will also be registered as a player for the Lions, having played for a number of Northern Premier League sides over recent seasons.
He replaces former boss Danny Ellis, who parted company with the club earlier this month following their 1-0 victory over Warrington Town in the FA Trophy second round.
“I’m thankful for the club for giving me this opportunity,” Phillips said.
“I will work tirelessly to make every success of this new challenge that we face.”
Discussing the appointment, Guiseley chairman Gary Douglas added: “Paul is experienced at this level of football and exactly what the team needs at this moment in time.
“The board, staff and players at the club will give Paul every resource available to us that he needs to be a success at the club."
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