This summer's tournament will be both of these nations' first Olympics, and they are in a group with experienced sides Brazil and China.
Zambia's preparation for the Tokyo Olympics has been disrupted by coronavirus restrictions that have limited the teams they could play against due to travel issues.
Therefore, Bruce Mwape's side have only played South Africa in the lead up to Wednesday's opening fixture, and that friendly was three months ago.
Zambia lost 3-1 to South Africa, who proved to be tough opponents having not lost a game since the end of 2019.
Many Zambian internationals have missed out on a place in the 22-strong squad for this summer due to injury or illness including Racheal Nachula, who would have become a two-sport Olympian having competed in the 400-metre event in 2008.
As for the Netherlands, they failed to qualify for the World Cup until 2015, and as that tournament was UEFA's designated qualifying competition for the Olympics, the Netherlands did not make it to the 1996, 2000, 2004, 2008 or 2012 Olympics.
The Dutch made it to their first World Cup in 2015 but, despite their round-of-16 exit being good enough for a post-World Cup mini tournament, Sweden sealed the last European spot for Rio 2016.
However, Sarina Wiegman's side are not to be underestimated at their first Olympics due to their success in the European Championships in 2017 and a long run in the 2019 World Cup.
The Netherlands won their first major international tournament at home in 2017 as they beat Denmark in the Euros, and they followed that up with a runners-up finish in France two years later.
Wiegman has been in charge of the Dutch national side since 2016 and this summer's Olympics will be her last tournament as Netherlands manager, before taking the job of England manager.
An emphatic 7-0 victory over Norway is the result which the Netherlands come into this tournament with, after their final friendly against South Africa was cancelled due to coronavirus restrictions.
Zambia captain Barbara Banda was the 2020 Chinese Women's Super League top goalscorer, after making her move from Logrono to Shanghai Shengli in January last year, and is expected to lead the line for her nation on Wednesday.
It is a young Zambian squad heading to the Olympics, with the oldest player being forward Hellen Mubanga at 26 years old, and 16-year-old Esther Siamfuko is the youngest member of any of the women's football squads at Tokyo.
The reigning European champions have a bundle of attacking threat they can utilise, including Lieke Martens, who won the treble with Barcelona last season, Lineth Beerensteyn, who helped Bayern Munich to their first league title in five years and Vivianne Miedema, who became the Women's Super League's all-time top goalscorer in October.
Zambia Women possible starting lineup:
Musonda; Mulenga, Khosa, Mweemba, Belemu; Kundananji, Chanda, Musase, Wilombe; Mubanga, Banda
Netherlands Women possible starting lineup:
Van Veenendaal; Janssen, Van der Gragt, Nouwen, Folkertsma; Groenen, Van de Donk, Spitse; Miedema, Martens, Beerensteyn
We say: Zambia Women 0-3 Netherlands Women
Despite neither team reaching an Olympics before now, the Netherlands have experience of winning a major international tournament which will be useful in their debut Olympics this summer.
Zambia's disrupted preparations will not have helped the side, and the quality in the Dutch front three could bring goals for the Oranges on Wednesday.