The standard byte order of 16/32/64 bit quantities for TcpIp transport is BigEndian.
The Berkely socket API defines functions ntohs/htons/ntohl/htonl to convert 16/32 bit quantities between host and network byte order.
AnswerMe: why was this chosen?
There was a coin flip. The LittleEndian partisans called tails. The coin (I believe it was a J.F.K. fifty cent piece once owned by J. Geils Band drummer Stephen Jo Bladd) landed on heads. The rest, as they say, is history.
You're pulling my leg! Surely it must be because the initial computers on the internet/arpanet were also BigEndian?