Hogg - with 72 global caps - is the most experienced man in the Scotland squad and takes over the captaincy from Stuart McInally, who led the side in the recent World Cup.
With 71 caps, the two-time Lion is the most experienced player in the 38-man squad named by Gregor Townsend for this year's championship, which start for Scotland with a trip to Dublin on 1 February.
The 27-year-old full-back replaces Stuart McInally, who led the side during last year's unsuccessful World Cup campaign.
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Steyn will join fellow South Africans WP Nel, Cornell du Preez and Allan Dell in the squad, which also includes former Border Bulldogs wing Byron McGuigan.
Edinburgh have 16 players in the squad, marking the greatest representation in Townsend's group of any club.
Head coach Townsend said: "Stuart is very passionate about playing for Scotland and he's determined to do all he can to improve Scotland".
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The Johannesburg-born Steyn, who qualifies for Scotland through his Scottish-born mother Gillian, previously represented the Scotland Sevens team and also played for Maties in the Varsity Cup. It's more about what he does every day at training.
"He really wanted to take on the honour and responsibility of being captain, which was a huge positive and - having heard his plans for how he would work as a captain and work to bring the best out of others, while being able to focus on his own game - meant it became a relatively straightforward decision".
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