RNA polymerase uses RNA as a template, and DNA polymerase uses a DNA template.
RNA polymerase binds to single-stranded DNA, and DNA polymerase binds to double-stranded DNA.
RNA polymerase does not need to separate the two strands of DNA in order to synthesize an RNA copy, whereas DNA polymerase must unwind the double helix before it can replicate the DNA.
RNA polymerase is much more accurate than DNA polymerase.
RNA polymerase can initiate RNA synthesis, but DNA polymerase requires a primer to initiate DNA synthesis.
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