Eastern side, you have florence, timmonsville (Honda), north, you have sumpter (AFB, Beckton Dickson), and western side you have Santee(tourist/hospitality). There is a lot of rural in between, most definitely.
Southernmost section, you have kingstree, rocks pond, holly hill - best options there are around kingstree.
Yeah, on the Williamsburg side, its a rural county and worse off than the Berkeley County Side..
Don't know what kind of work you are looking for, but there's a Federal Prison on 521 that runs up the Williamsburg side of the lake - its just off the intersection of 52 and 521.
Pineville area can commute to Kingstree, St. Stephen, Moncks Corner. Greeleyville side makes you more likely to run up to the Manning, or Kingstree area, or over to the prison I mentioned.
Kingstree has a few large employers, but the textile and latex glove factories have long gone. Martex or Martech is a high-tech employer in the area. There's also a lot of mechanical / metalworking contractors in the area.
Opportunitites are out there, but a lot of slim pickins now. I'd imagine the williamsburg unemployment is in the 12-teens%, Berkeley around the 10%...
With Boeing coming into the north Charleston area, maybe there'll eventually be some spillover subcontractors coming into the surrounding areas.