Some early trades of bitcoins for physical things you need to know.
theymos sold bitcoin for $0.003/
BTC.
SeeBut I believe the first actual realization of Bitcoin's real value as a payment network was when the Silk Road was built by Ross Ulbricht. There was a gap in the online drugs market, which obviously no financial institution would service. Bitcoin filled that gap - plus made that market more efficient and payments became a little less frictionless.
Many people in BitcoinTalk probably consider Ross Ulbricht a mere criminal because he built something illegal. But from another point of view, he's also an accelerationist who wanted to change the exisiting state of affairs.