Vladimir Makei, who had held his post since 2012, was due to meet his Russian counterpart Sergey Lavrov next week.
Baku and Yerevan accuse each other of opening fire on border settlements on Monday as representatives from both countries hold US-mediated talks.
A ceasefire between Armenia and Azerbaijan holds, according to Armenian officials, following two days of fighting that left dozens of soldiers killed from both sides.
Angry protesters demanding PM Nikol Pashinyan step down try to storm parliament as the latest clashes between the Caucasus neighbours leave over 150 soldiers dead, most of them Armenians.
Rescue workers and volunteers in civilian clothes searched for victims who might be trapped under slabs of concrete and twisted metal.
Almost 60 people return to Zangilan district, which they had to flee in 1993 when Armenian forces attacked and occupied it, killing thousands of people and displacing some 30,000 from the area.
Special representatives of the neighbouring countries will convene in Vienna to discuss steps towards rapprochement.
Leaders of Azerbaijan and Armenia agree in Brussels meeting to work further on a peace plan that has stoked a wave of protests in Yerevan over opposition claims that PM Pashinyan mishandled the conflict with Baku.
Opposition parties have been staging rallies demanding Prime Minister Nikol Pashinyan's resignation over his handling of Karabakh conflict with Azerbaijan.
Former high-tech industry minister Vahagn Khachaturyan was elected as the fifth president of Armenia, receiving 71 votes in the second round of the parliamentary vote.
Pegasus Airlines and Armenia's FlyOne will operate flights from Istanbul to Yerevan thrice a week, marking the first step towards normalising ties between the two countries.
Turkiye and Armenia agree to discuss steps to normalise relations appointing special envoys and resuming flights.
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