The Cairo giants' skipper notched what proved to be the winner in the 27th minute as Zamalek received a major boost ahead of Monday's Cairo derby against recently-crowned Egyptian champions Ahli.
The win moved Zamalek to second place with 62 points, just one ahead of third-placed Ismaili as both sides compete for the final CAF Champions League spot.
Amr Zaki almost put the hosts in front after ten minutes when Osama Hassan's cross from the left-flank was mis-cleared by an Ittihad defender into the path of the Egypt striker, whose close-range shot struck the bar.
The men in white dominated in terms of possession in the first-half but rarely threatened Ittihad's net.
Emam broke the deadlock in the 27th minute after he cut ahead of his marker to receive Wael Al-Qabani's cross with a brilliant left-footed strike into the top corner of the net.
Zamalek could have doubled the lead two minutes before the interval when Gamal Hamza's superb chip beat the offside trap and picked out Mohamed Aboul-Ella inside the area but the midfielder's effort was blocked by the advancing keeper.
The second-half was a one-way traffic as Zamalek wasted a host of opportunities to kill-off Ittihad's hopes.
Zamalek's right-back Youssef Hamdi fired a fierce drive from inside the area but was denied by the post six minutes after re-start.
Ittihad's only real opportunity in the match came in the 56th minute when a cross from the right-flank was headed just wide by the unmarked Daudu Alilu.
Five minutes past the hour mark, substitute Mahmoud Abdul-Razeq 'Shikabala' released Aboul-Ella with a deft through pass before the latter crossed to Hamza, whose shot was blocked by Ittihad defenders.
Zaki was involved in an altercation with teammate Shikabala eight minutes from time after an individual effort by the latter frustrated the former ENPPI striker.