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It is inaccurate, food manufacturers are allowed about 20% error margin when measuring calories. Calories have nothing to do with what our bodies do with the material we eat, since everything is a chemical process and we aren't closed systems. When we mobilize fat we create ketone bodies which are exhaled in our breathing, how do you propose to measure 'caloric expenditure' then? It is far too reductive.
Calories on a label are not the calories in the metabolic equation, so I don’t see how that is relevant here. Calories in are calories absorbed by the body, which is some subset of those taken in. Some come right back out the other side; we don’t count those. To say calories have nothing to do with it is bonkers to me. It is precisely the chemical process to which you refer. When we expend energy / heat / calories, we get that from food and drink. Yes, more immediate from one of the three major energy distribution mechanisms, but it all comes from what we put in. Then the carbon atoms stripped off of saccharides are bonded to oxygen and exhaled as CO2.
And all this to say, one cannot gain weight while eating fewer calories than being expended, reductive or not.
The calories on the label are what is used to make decisions when it comes to using CICO to decide what to eat, which is why it's relevant. I see now where you are coming from though, because I'm speaking from a pragmatic stand point, but yours is a theoretical one.
We do however appear to be in agreement, too. Due to these chemical processes CICO is highly reductive and pretty pointless for losing body fat, because what our bodies do in response say to 100 kcal of sucrose and 100 kcal of protein is entirely different, and result in entirely different biological outcomes.