Relating to or expressing religious devotion; used for prayers or spiritual practices.
From 'devotion' plus the suffix '-ary' (meaning 'relating to' or 'of the nature of'). Similar pattern to 'missionary' or 'voluntary,' all using Latin-based suffixes to create adjectives.
This is a rare word that shows English's weird flexibility—'devotionary' and 'devotional' mean basically the same thing, but 'devotionary' sounds more archaic and formal, which is why you'll find it in old hymn books but almost never in modern writing.
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