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West Mercia police said two men from Wolverhampton aged 39 and 41 were charged with conspiring to commit grievous bodily harm, along with three men aged 25, 26, and 22.
They are due to appear at Kidderminster Magistrates' Court to be tried over the suspected attack, which saw corrosive substance being "sprayed or thrown" at the toddler on Saturday at 2:15pm in a Home Bargains in Worcester. The defendants cannot be named for legal reasons.
The victim was brought to the hospital with serious burns to his face and arms.
The child has now been released and is under police protection, but the long-term repercussions the injuries may have on his health are yet unknown.
Police refused to comment on speculation the child was at the center of a family dispute, but they did say they thought the alleged attack was deliberate.
Local MP Robin Walker called it "horrific" and said the "shock will be universal."
Comment: The BBC reports the father of the boy is among the five men charged in the case. Further details about the case have yet to emerge.