That would be possible if you use a Boost converter.
The output power of this converter will NEVER be more that in input power.
You will have to deal with the efficiency of the converter.
When you are using an EXTERNAL power-supply, you can switch things with the higher voltage.
Since Im very slow to understand things and new to electronic, Can you please elaborate above statements in simple ways . preferably with example. so that I understand.
First of all, you can not switch anything directly from the USB port.
You will need some kind of interface, that communicates with the USB port.
The output of the interface might drive a trasistor.
The collector of the transistor may have a higher voltage as the USB powersupply.
If you want to switch , let's say , a 12 Volts relay, you will need a 12 Volts power-supply to power the relays.
The relays can be connected between the collector of he transistor and the +12 Volts of the power-supply.
The - of the power-supply needs to be connected to the - of the interface and emittorof the transistor.