For me, this makes 60% of the market at least. A 1% to 60% is not a small difference, it is a real gap.
Don't forget that success isn't always connected with technical things (very good example is MySQL :-)) - PostgreSQL needs a good marketing, clear strategy and identity. But for sure Win32 port will be a huge step.
There are other databases which have Win32 native version and aren't so popular (like Firebird...)... So my proposition to PostgreSQL's team is to think also about SMI -> Strategy Marketing Identity...
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