和 has five readings total. This entry is hé (the broad 'and / harmony / peace / Japan' sense — by far the most common). The others: hè = to chime in with a poem or song (
附和); huó = to knead dough (
和面); huò = to mix ingredients or water rinses (
搅和); and a niche hú used only in mahjong and cards meaning 'to complete a winning hand' (
和牌).