Am I correct to assume that every electrical system on an aircraft can be manually switched OFF/ON by the Pilot OR is there indeed any system, on which the Pilot does not have the ability to switch OFF/ON ?
One example of a system that cannot be switched off by the pilot that is probably more common to all other airframes than just the one airframe I'm indicating.
Whenever electrical power is applied to a Gulfstream G550, whether it is powered by battery, generators, an apu, or some external power source, each engine's FADEC Electronic Engine Control (EEC) computer will be powered and the pilot can not switch them off.
The pilot could only indirectly turns them off by switching off all power sources.
However, when the engines are running, he can't even do that since there is an engine-driven generator dedicated to powering the EECs in the event of a total power loss.
In fact, while the engine is running or even windmilling above 35% rpm, the EEC's dedicated generator is supplying all power to the EEC and there is no switch or circuit protection that can be manipulated by the pilot to interrupt it.
On an R22 helicopter (I quote from the Pilot Operating Handbook):
Each tach, the governor, and the low rotor RPM warning horn are on separate circuits. Either the battery or the alternator can independently provide power to the tachs. A special circuit allows the battery to supply power to the tachs even if the master battery switch is off.
It is clear that the designers intend the the tachometers should work at all times, and there is no "off switch".
To Falstro's point, the procedure for an electrical fire in flight includes turning off the alternator and battery master, and this is the precise moment when I am pleased to find that the tachometers are still working, since the governor and RPM warning horn are not.
It is true that there is also a circuit breaker for the tachometers, but there is no procedure, emergency or otherwise, which demands for these to be pulled. The only time I have ever known these to be used is by instructors to simulate emergencies for training purposes.
The R22 is a pretty simple system and I don't know much about airliners but I imagine that it's impossible to access the flight data recorders in flight and I'm sure the designers try quite hard to make sure that they have power under all circumstances including catastrophic aircraft failure and hijack.
The pilot is generally given ultimate control over everything in the plane, when it comes down to it. Just like your car, they have to be able to shut everything down at the end of a flight. Take a look at this 737 classic overhead panel:
You will notice all important switches have an "OFF" position. The black and red switch covers protect the main power connection switches, which you generally want to be "ON" during the flight. The BAT switch at the top connects the battery to the DC electrical bus. The switches below that control the switching of standby power, and the connection to the engine generators. At the bottom are the controls to transfer between different power sources.
Of course there are many other switches for different systems. Which systems have dedicated switches will depend on the make and model of the aircraft. As others have commented, some low level systems like engine control may be absolutely necessary for some things to function, and will not be easy to switch off.
As ratchet freak commented, they also have access to the circuit breakers. Here is another picture from the 737, behind the first officer's seat. The pilot's handbook has instructions for what breakers should be switched off in what circumstances. Outside of those instructions, the effect on other systems of pulling one breaker could have unexpected consequences. The circuit breakers can be used to switch off equipment as a last resort.