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Simon,
What is the serial port number and what are the serial port settings you see when you use it both direct and through a hub ?
What OS are you using ? If its an early version are the USB/RS232 adapter drivers installed for each port in use ?
Do you know what chipset is in the USB/serial adapter and in the USB Hub ? - eg Prolific, FTDI - could be some sort of incompatibility.
I would be inclined to delete it via Device Manager and reinstall it and see if that makes a difference.
Then maybe update to latest version of drivers just in case something is broken.
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