In the week which saw previous boss Russell Slade sacked, the seventh departure from The Valley since March 2014, Charlton started on the front-foot as Jason Pearce's header hit the bar early on.
The Addicks took the lead in the 30th minute through a superb Josh Magennis header, with the Northern Ireland international finding the far corner from Morgan Fox's cross.
Charlton - with caretaker boss Kevin Nugent overseeing proceedings - doubled their advantage a minute before half-time, as Fox's pass found Nicky Ajose who slotted the ball past Jak Alnwick in the Port Vale goal.
The visitors, as expected, came out after the break searching for a goal back but Nathan Smith's flicked effort that evaded Declan Rudd's goal was the closest Bruno Ribeiro's side came to scoring.
The win was only Charlton's fifth in League One this campaign and sees them rise to 14th in the table, while Port Vale remain without a win on the road since early October.
Report supplied by Press Association.
Match ends, Charlton Athletic 2, Port Vale 0.
Second Half ends, Charlton Athletic 2, Port Vale 0.
Attempt missed. Jordan Botaka (Charlton Athletic) right footed shot from outside the box is close, but misses to the left.
Substitution, Charlton Athletic. Ezri Konsa Ngoyo replaces Ademola Lookman.
Attempt missed. Nathan Smith (Port Vale) right footed shot from very close range is close, but misses to the left following a corner.
Corner,  Port Vale. Conceded by Jason Pearce.
Attempt blocked. Paulo Tavares (Port Vale) right footed shot from outside the box is blocked.
Attempt missed. Martin Paterson (Port Vale) right footed shot from the centre of the box is close, but misses to the right.
Hand ball by Kjell Knops (Port Vale).
Foul by Jason Pearce (Charlton Athletic).
Martin Paterson (Port Vale) wins a free kick on the right wing.
Foul by Ademola Lookman (Charlton Athletic).
Remie Streete (Port Vale) wins a free kick in the defensive half.
Attempt saved. Martin Paterson (Port Vale) left footed shot from outside the box is saved in the bottom left corner.
(Charlton Athletic) wins a free kick in the attacking half.
Foul by Anton Forrester (Port Vale).
Patrick Bauer (Charlton Athletic) wins a free kick in the attacking half.
Foul by Martin Paterson (Port Vale).
Substitution, Port Vale. Anton Forrester replaces Sam Kelly.
Substitution, Charlton Athletic. Brandon Hanlan replaces Josh Magennis.
Patrick Bauer (Charlton Athletic) wins a free kick in the defensive half.
Foul by Martin Paterson (Port Vale).
Foul by Jason Pearce (Charlton Athletic).
Martin Paterson (Port Vale) wins a free kick in the defensive half.
Ademola Lookman (Charlton Athletic) wins a free kick in the attacking half.
Foul by Ryan Taylor (Port Vale).
Attempt blocked. Alex Jones (Port Vale) right footed shot from the centre of the box is blocked.
Foul by Fredrik Ulvestad (Charlton Athletic).
Martin Paterson (Port Vale) wins a free kick in the defensive half.
Foul by Nicky Ajose (Charlton Athletic).
Ryan Taylor (Port Vale) wins a free kick on the left wing.
Corner,  Port Vale. Conceded by Morgan Fox.
Substitution, Port Vale. Quentin Pereira replaces Jerome Thomas because of an injury.
Substitution, Charlton Athletic. Jordan Botaka replaces Johnnie Jackson.
Attempt blocked. Sam Kelly (Port Vale) right footed shot from outside the box is blocked.
Delay in match Jerome Thomas (Port Vale) because of an injury.
Foul by Patrick Bauer (Charlton Athletic).
Alex Jones (Port Vale) wins a free kick in the attacking half.
Attempt missed. Sam Kelly (Port Vale) left footed shot from outside the box is close, but misses to the right.
Corner,  Port Vale. Conceded by Jason Pearce.
Managerless Charlton secured their third home league victory in as many matches with a 2-0 win over play-off chasing Port Vale.