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The canon of the Old Testament that Catholics use is based on the text used by Alexandrian Jews, a version known as the "Septuagint" and which came into being around 280 B.C. as a translation of then existing texts from Hebrew into Greek by 72 Jewish scribes .
The deuterocanonical books were, though, debated in the early Church, and some Fathers accorded them higher status than others (hence the Catholic term for them: "deuterocanonical," or what St. Cyril of Jerusalem called "secondary rank," as opposed to the other books which are called "protocanonical"). But all the Fathers believed as did St. Athanasius, who, in one of his many Easter letters, names the 22 Books all Christians accept and then describes the deuterocanonicals as "appointed by the Fathers to be read by those who newly join us, and who wish for instruction in the word of godliness." Church Councils listed and affirmed the present Catholic canon, which was only formally closed at the Council of Trent in the 16th century.
In the 16th c., Luther, reacting to serious abuses and clerical corruption in the Latin Church, to his own heretical theological vision ,see articles on sola scriptura and sola fide, and, frankly, to his own inner demons, removed those books from the canon that lent support to orthodox doctrine, relegating them to an appendix. Removed in this way were books that supported such things as prayers for the dead (Tobit 12:12; 2 Maccabees 12:39-45), Purgatory (Wisdom 3:1-7), intercession of dead saints (2 Maccabees 15:14), and intercession of angels as intermediaries (Tobit 12:12-15). Ultimately, the "Reformers" decided to ignore the canon determined by the Christian Councils of Hippo and Carthage and resort solely to those texts determined to be canonical at the Council of Jamnia.
It is the Church that is the "pillar and ground of Truth" (1 Timothy 3:15)! Jesus did not come to write a book; He came to redeem us, and He founded a Sacramental Church through His apostles to show us the way. It is to them, to the Church Fathers, to the Sacred Deposit of Faith, to the living Church that is guided by the Holy Spirit, and to Scripture that we must prayerfully look.
Luther wanted to remove the Epistle of James, Esther, Hebrews, Jude and Revelation. Calvin and Zwingli also both had problems with the Book of Revelation, the former calling it "unintelligible" and forbidding the pastors in Geneva to interpret it, the latter calling it "unbiblical".
This Council, among other things, simply affirmed the ancient accepted books in the face of Protestant tinkering. How could Luther have relegated the deuterocanonical books to an appendix if they hadn't already been accepted in the first place?