Starkovs, 61, will replace Marians Pahars who stepped down in March after a humiliating defeat to Georgia in March.
Starkovs was the head coach of the Latvian national team from 2001 to 2004. He coached the Latvian football team that historically qualified for the 2004 European Football Championships (EURO 2004).
He returned to coach the Latvian national team in 2007, but stepped down again in 2013.
Latvia has currently dropped to 124th place in the FIFA ranking, its lowest result ever.