It is possible for high voltage DC to be made safe. Currently, techniques to do so are neither cheap nor off-the-shelf.
For example, imagine I want a 3000 volt DC wire to power a portable air conditioner. The air conditioner will be 10 kilowatts, so 3.3 amps. The wire can be thinner than headphone cables (two 0.3mm conductors, +-1500 volts, 150um PTFE coating) if desired.
Obviously, with such a thin insulation, the system needs to be human safe when chewed through by a baby. To ensure that, the current flow through the baby must be under 1 milliamp, or 10 milliJoules through the baby's heart. That can be ensured by tracking the current through each conductor, accurate to 1 milliamp, and shutting off the supply if there is ever more than 1 milliamp unaccounted for (either to earth, or to the other conductor). When the shutoff occurs, it must therefore happen within 1 microsecond (assuming the worst case fault, that is all three amps direct to the baby's heart). That in turn puts capacitance and therefore length limits on the cable - it wouldn't be possible for this cable to be safe longer than ~1000 feet.
TL;DR: It is very possible, with today's technology, to design very high voltage DC systems safe enough for use within a home. However, no hardware available off-the-shelf yet can do this, due to no demand.