Yes, it would work, and I have used redundant heating oil in my vehicle several times. BUT that vehicle is a tractor and is allowed to run on red diesel without the duty. Putting heating oil in your car will leave a tell-tale residue which can be detected by HM Customs even if you filled up ever after with duty-paif fuel. You'd be amazed how many spot checks they do!
Ordinary home heating oil is 28 second oil - Red diesel is 32second - has a different Octane/cetane rating - would damge the engine over a long period of time.