The Chile international agreed to join the Gunners in the summer for a reported £35m, and after making his first appearance in a second half cameo during Saturday's 5-1 win over Benfica, Sanchez was named in the team that will take on the Ligue 1 runners-up at the Emirates Stadium.
Arsene Wenger elected to field a much stronger line-up than that of Saturday's comfortable win, with regulars Laurent Koscielny, Mikel Arteta, Jack Wilshere and Olivier Giroud coming into the starting XI. They were joined by another new signing making his first start in right-back Mathieu Debuchy, while £16m centre-back Calum Chambers retained his place in the middle of the defence.
The pairing of Chambers and Koscielny would certainly face a stiff test as Colombian striker Radamel Falcao was named in the Monaco starting line-up for the first time since he suffered a ruptured cruciate ligament back in February, ruling him out of the World Cup.
Arsenal: Szczesny, Debuchy, Chambers, Koscielny, Monreal, Arteta, Ramsey, Wilshere, Cazorla, Sanchez, Giroud.
Subs: Martinez, Miquel, Hayden, Bellerin, Coquelin, Flamini, Oxlade-Chamberlain, Zelalem, Akpom.
Monaco: Subasic, Carvalho, Dirar, Moutinho, Falcao, Ocampos, Bakayoko, Ferreira-Carrasco, Echiejile, Kondogbia, Raggi.
Subs: Fabinho, Kurzawa, Abnennour, Berbatov, Germain, Isimat-Mirin, Martial, Toulalan, Bahamboula, Diallo, Caillard.
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