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Let us say you have a Wizard that decides to ready an action that if a creature charges them and reaches 10 foot away, that the wizard would then cast a spell, let us say Shocking Grasp, 5-foot step to close the gap and deliver the spell.
Image Equivalent:
O is Wizard, X is enemy
O------X - Starting position
O-X----- - Charging point of triggered Readied Action
-OX----- - Ready action Trigger to cast Shocking Grasp and 5-foot step to deliver the spell
Would this be possible since it is availible to do a 5-foot step in a readied action?
Yes. As long as you take no other movement that round, you can take a 5' step during your readied action. That's the only stipulation. Otherwise this works just fine.
Keep in mind a creature with reach would still threaten you, so you might need to cast defensively. Although I believe your questions is referring to them reaching a point 10 feet from you, not having 10 foot reach.
But yes, short answer, you can do it.