Since radiocarbon dating can only be used to determine the age of carboniferous materials such as fossils, not stones, to do what you suggest an archaeologist would use the rock strata to determine the age of artifacts. If you find a stone tool on the same layer and in the same area as hominid fossils you can determine the age of the fossils through radiocarbon dating or more advanced methods and assume the entire site and stone tool comes from the same age.
Thermoluminescence only works on pottery and objects that were fired. Using dated fossils to assume the dates of objects in the same strata is the method by which artifacts are dated.
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