Ecuador came from behind to stun Portugal, while Sergio Aguero and Gonzalo Higuain were on target as Argentina beat Sweden on Wednesday.
Cristiano Ronaldo and Helder Postiga had appeared to have steadied Portugal, who went behind to an Antonio Valencia goal in the second minute in Guimaraes.
But Paulo Bento's men were set for a shock friendly loss as a Joao Pereira own goal and Felipe Caicedo's 70th-minute effort saw Ecuador to the surprise 3-2 win.
In an entertaining affair in Solna, Argentina edged Sweden 3-2 but were in control for the most part.
A Mikael Lustig own goal gave the South Americans the lead before Jonas Olsson cancelled out the opener in the 18th minute.
Aguero and Higuain were on the scoresheet as Alejandro Sabella's men took control of the encounter, and they held on despite Rasmus Elm's stoppage-time goal.
Mario Mandzukic, Darijo Srna, Nikica Jelavic and Mladen Petric netted in Croatia's 4-0 thrashing of South Korea.
Elsewhere, a Shinji Okazaki brace helped Japan to a 3-0 win over Latvia, while Dusan Tadic scored twice in Serbia's come-from-behind 3-1 victory against Cyprus.
The Czech Republic were 2-0 winners against Turkey, Macedonia were surprisingly comfortable 3-0 victors over Denmark and Dries Mertens struck a late winner as Belgium overcame Slovakia 2-1.
Chile held on for a 2-1 win over Egypt, Lior Refaelov's late goal gave Israel a 2-1 victory against Finland and Gareth Bale was on the scoresheet in Wales' 2-1 defeat of Austria.
Hungary and Belarus played out a 1-1 draw, Bosnia and Herzegovina easily disposed of Slovenia 3-0 and Ukraine were 2-0 winners against Norway.
The Republic of Ireland were too good for Poland in a 2-0 win and Romania scored twice in the last 10 minutes to beat Australia 3-2.
Malta and Northern Ireland saw out a scoreless draw, as did Greece and Switzerland, while Russia overcame Iceland 2-0, Scotland beat Estonia 1-0 and Georgia defeated Albania 2-1.
Kazakhstan recorded a 3-1 win over Moldova and Azerbaijan posted a 1-0 win over Liechtenstein.