Depends slightly on the map. I always put a lot of though into this.
Many people don't assign second skills at all to their masons. Not me. I have to fill all skill slots to avoid unspeakable agony for myself on embark.
On maps with no aquifer and decent amounts of wood I'll go with this or similar variants (at least next time, I'm constantly experimenting):
My Craftsdwarf: 5 Miner/4 Stone Crafter/1 Bone Carver (Mining is done mostly in the beginning, setting up the starting fortress, and later if necessary; other times he's going to be my prime producer of dwarfbux to trade with)
My Bossdwarf: 5 Miner/1 Appraiser/1 Judge of Intent/1 Organizer/1 Record Keeper/1 Negotiator (as recommended by wiki, though I occasionally consider giving Record Keeper to some other dwarf to give him another rarely used Novice Skill)
I like to carve out large parts of my fortress right in the beginning instead of smaller lodgings, so I don't want to wait for lower-skilled minerdwarfs to take bloody ages. Thus, two Proficient Miners.
My Masondwarf: 5 Mason/1 Building Designer/1 Animal Trainer/3 Herbalist (Building Designer because he'll build most buildings that need this himself anyway, I can get a dedicated Building Designer later. Animal Training because he can do that with the starting dogs before he even has access to stone; same for Herbalist; if I need some herbalism done later I let immigrants do it. It's hard to find decent skills for this guy, but that's what I go with usually.)
My Armorsmith: 5 Armorsmith/4 Planter/1 Fish Cleaner (This guy will be occupied mostly with his planting and fish cleaning tasks, BUT once the metal industry kicks in, he's going to be the best Armorsmith I can get my hands on! Especially if I don't have magma I'm not in the mood to train immigrant guys to become this good, and I also can't rely on strange moods to give me legendaries.)
My Weaponsmith: 5 Weaponsmith/4 Carpenter/1 Woodcutter (Yeah yeah, hear me out. Carpentry is not usually as much of a fulltime job as being a Mason is, and a Novice Woodcutter is all I need. This guy will have periods of downtime, and in these he can make more kickass weapons than any immigrant. When immigrants come into play, I'd much rather have immigrant carpenters churning out subquality beds than immigrant weaponsmiths churning out subquality weapons. If wood is very sparse, even less reason to have a full-time Carpenter!)
My Provisiondwarf: 5 Grower/3 Brewer/2 Cook (Once immigrants help him he can become a dedicated Brewer or Cook as needed.)
My Fisherwithhiddentalentsdwarf: 3 Mechanic/2 Fisherdwarf/1 Metalsmith/4 Skill points I'd like to discuss (He's going to have stuff to do right from the beginning - Fish, fish fish, and give one of the other dwarfs something to do. I don't go for traps, so 3 Mechanic is all I need. You'll never need more than a Novice Metalsmith even if you do plan on having an early metal industry, considering quality levels don't mean jack shit for metalsmith items.)
The point people have made about bags is actually a very good one, so I might try to include this in the skill lineup of my last dwarf - though I think Tresher/Weaver/Clothier is more sensible than going for leather bags, as wild animals can easily chew through a hunterdwarf. Better to lose expendable immigrants hunting much later. On maps with magma and sand I will include Glassmaker too - Glassmaking will actually serve to relieve my Mason from some of his stress.