The seven-time Formula 1 world champion clocked 1:16.514 to take the top spot at the Autódromo Hermanos Rodríguez, edging Russell by just 0.009 seconds in an extremely close battle.
The achievement marked Hamilton's first pole position since the 2023 Hungarian Grand Prix and the 105th of his Formula 1 career.
Ferrari also enjoyed a strong qualifying session, with Charles Leclerc completing the top three after recording 1:16.633, 0.119 seconds behind his team-mate.
Max Verstappen finished fourth with a time of 1:16.692, while championship leader Kimi Antonelli secured fifth place for Mercedes.
Hamilton initially faced a challenge in the final qualifying session after Leclerc set the early benchmark. Russell subsequently moved to the top of the timesheets with his final attempt, but the British Ferrari driver produced an outstanding lap to snatch pole by the smallest of margins.
Speaking after the session, Hamilton expressed his delight at securing his first pole position since joining Ferrari.
Piastri suffers disappointing qualifying exit
McLaren endured a difficult afternoon, with Lando Norris managing only sixth place despite showing impressive pace earlier in the weekend.
His team-mate Oscar Piastri suffered an even bigger setback after failing to progress beyond Q2, finishing 13th in the classification.
Isack Hadjar qualified seventh for Red Bull, ahead of Liam Lawson in eighth and Arvid Lindblad in ninth. Pierre Gasly completed the top 10 for Alpine.
Fernando Alonso also experienced disappointment after a suspected water-pressure problem linked to the energy recovery system forced him to stop during Q1, leaving him 18th.
Mexico City Grand Prix qualifying results
• 1. Lewis Hamilton (Ferrari): 1:16.514
• 2. George Russell (Mercedes): 1:16.523
• 3. Charles Leclerc (Ferrari): 1:16.633
• 4. Max Verstappen (Red Bull): 1:16.692
• 5. Kimi Antonelli (Mercedes): 1:16.707
• 6. Lando Norris (McLaren): 1:16.824
• 7. Isack Hadjar (Red Bull): 1:16.900
• 8. Liam Lawson (Racing Bulls): 1:17.029
• 9. Arvid Lindblad (Racing Bulls): 1:17.117
• 10. Pierre Gasly (Alpine): 1:17.153
Hamilton will now start Sunday's Mexico City Grand Prix from pole position as he targets another victory for Ferrari, while Russell and Leclerc will line up immediately behind him.