The hosts reached the semi-final of Germany's main domestic cup in 1993, while the visitors were runners-up in 2001.
Match preview
Chemnitzer, who finished fifth in Regionaliga Nordost last season as they failed to return to the third tier of German football for the second successive season, do have pedigree in the DFB-Pokal.
Hertha Berlin's reserve team prevented them from reaching a maiden final in the aforementioned 1992-93 campaign, but Die Himmelblauen have progressed past the first round in six of the seasons since that record run deep into the competition.
Coach Christian Tiffert's primary focus will be guiding his team back into 3. Liga, where they spent seven successive seasons between 2011 and 2018, with the long-term goal being returning to 2. Bundesliga, which they were last a part of in 2001 before running into financial difficulties.
Four successive wins and clean sheets in pre-season heading into Monday's test against Bundesliga side Union Berlin will do no harm to Chemnitzer's belief that they can carry out a major upset.
In many ways, Union Berlin are the model club for those in the lower divisions to aspire to having gone from strength to strength since being promoted to the Bundesliga for the first time in the club's history in 2019.
Urs Fischer, who secured promotion in his first season in charge of the club after taking over in 2018, has overseen gradual yet remarkable progression in the shape of 11th, seventh and fifth-placed finishes in Germany's top tier.
Last season the former East Berlin side were only one point away from securing Champions League football for the first time in the club's history, but instead they will compete in the Europa League for the first time since the 2001-02 campaign, which was earned as a result of the aforementioned DFB-Pokal final defeat to Schalke 04 in the previous season.
Fischer will undoubtedly have his eyes on securing Union Berlin's first ever major silverware at some point during his time in charge, while ensuring they continue to progress on the domestic and European stages.
In the meantime, though, the 56-year-old will be aware of the danger Chemnitzer pose his team on Monday, but five wins from seven pre-season friendlies suggest Die Eisermen are ready and raring to go once again.
Chemnitzer pre-season form:
Union Berlin pre-season form:
Team News
Chemnitzer will be without Jasin Jusic and Furkan Kirciek due to serious knee and muscle injuries respectively.
Tiffert could choose the same XI which dispatched FC Viktoria 1889 Berlin 2-0 in a friendly last weekend, with Tobias Muller captaining the side.
Union Berlin, meanwhile, will travel without Timo Baumgartl as the defender continues to recover from his testicular cancer diagnosis.
Fabio Schneider is thought to be close to returning from his medial collateral ligament injury, but the 19-year-old will almost certainly not be risked for Monday's trip to Chemnitz.
Fischer will be keen to utilise the same XI which impressively defeated Nottingham Forest 1-0 in the side's final pre-season outing, with new signing Jordan Siebatcheu scoring after his move from Young Boys.
The 26-year-old will need to hit the ground running after Taiwo Awoniyi's £17m departure to Forest.
Chemnitzer possible starting lineup:
Jakubov; Berger, Zickert, Campulka, Walther; Muller, Kurt; Roscher, Pelivan, Pagliuca; Brugmann
Union Berlin possible starting lineup:
Ronnow; Jaeckel, Knoche, Heintz; Trimmel, Khedira, Haberer, Griebelmann; Becker, Haraguchi, Siebatcheu
We say: Chemnitzer 0-2 Union Berlin
We expect Chemnitzer to give their Bundesliga opponents a tough encounter in both sides' first competitive games of the season.
The visitors should ultimately have a little too much nous and quality, though, as they look to build on last season's remarkable league finish by juggling three competitions.