Both nations have turned heads so far in Brazil, delivering eye-catching performances to bring about the demise of reigning champions Spain.
The Netherlands claimed arguably the result of the competition to date by trouncing Vicente Del Bosque's men 5-1 last Friday, coming from behind to stun their opponents with a devastating display of pace and penetration.
Yet Chile also impressed when earning a 2-0 victory over Spain in the Maracana on Wednesday, the energy and high-pressing of Jorge Sampaoli's side proving pivotal to that result.
Although Chile and the Netherlands were made to work hard in their respective games against Australia, each did enough to secure three points.
However, while there is no longer any doubt over who will qualify from Group B, with Australia and Spain already eliminated, there will still be plenty at stake in Sao Paulo for the two teams going through to the knockout stages.
The winner of the group is set to avoid a daunting last-16 clash with Brazil, unless the hosts - who face Cameroon later on Monday - unexpectedly concede top spot in their pool to either Mexico or Croatia.
For that reason, the Netherlands and Chile will be particularly eager to maintain their momentum and make it three wins out of three.
A draw would see Louis van Gaal's men remain ahead of Chile due to their superior goal difference, but the chances of the Netherlands adopting a cautious approach appear slim.
The attack-minded Dutch have already found the net eight times, a tally matched only by France, while forwards Arjen Robben and Robin van Persie are among the World Cup's joint-leading scorers with three goals apiece.
Captain Van Persie will be absent for the Chile fixture due to suspension, having picked up two yellow cards in as many matches, and defender Bruno Martins Indi could also miss out after sustaining a concussion in the 3-2 win over Australia.
It is possible that Chile coach Sampaoli will opt to rest midfielder Arutro Vidal, who is on a yellow card and still working his way back to full fitness after undergoing knee surgery last month.
Vidal may be joined on the sidelines by Charles Aranguiz, a scorer in the famous success against Spain, who has a knee strain and a yellow card to his name.
