The Udinese forward came off the bench during Italy's tournament opener against Spain and scored with virtually his first touch to give his country the lead.
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"He must be a starter and then Prandelli can choose whether to play [Antonio] Cassano or [Mario] Balotelli alongside him," the Azzurri's hero at Italia 90 told Gazzetta dello Sport.
"The top-flight career of players has been prolonged, but then, we have already seen that with Di Natale. With his first touch, he is capable of scoring goals.
"He also has character, experience, outstanding technique and in recent seasons he has scored an avalanche of goals.
"In Italy one does not become the capocannoniere by luck. In short, I would always play him."
It is believed that Balotelli is more likely to be dropped than Cassano, and Schillaci admits that he can understand why, given their respective displays against the Spanish.
"I liked Antonio; he moved well," the former Juventus and Inter forward mused. "Mario, instead, looked a little sad. He is, however, technically very strong and knows how to fight. I think he has a great future ahead of him.
"But Toto [Di Natale] is capable of scoring impossible goals; he must be a starter."
Italy's meeting with Croatia in Poznan is scheduled to get under way at 18:00CET.