Comparing a V6 to an I4 may be apples to oranges in a technical sense, but it is a very real comparison when a person goes to shop for a car. Often times, a manufacturer will package the same sedan body with both a V6 and an I4. Honda Accords and Toyota Camrys immediately come to mind, and many others.
Most of the time, the V6 will be of larger capacity than the I4, but commands a price premium, higher fuel consumption and servicing costs. However, the V6 will be smoother to drive and torquier and would be a better match to an automatic transmission. Horsepower numbers may be fairly close, but not torque figures, unless the I4 is turbocharged or supercharged.
Technologically, both V6s and I4s are fairly close. You can get both with variable valve timing, high compression, excellent engine management systems... the list goes on. The V6 powerplants are usually heavier, but the engineers also work hard to reduce weight on them wherever possible such as composite intake manifolds, aluminium accessory mounting brackets etc. I also have a feeling that a V6 engine will usually have a higher "development budget" compared to an I4, seeing that the V6 is often viewed as a more premium engine.