Short answer
5pm is generally considered late afternoon, not evening. On a wedding invite, you can write 'afternoon' if the ceremony is before 5pm, or 'evening' if it starts at 6pm or later. For a 5pm start, 'afternoon' is safer, but 'late afternoon' is clearest.
There is no official rule, but in the UK, afternoon usually means from midday to around 5pm or 6pm. Evening usually starts around 6pm or 7pm. A 5pm ceremony sits right on the edge, so you need to decide what message you want to send to guests.
If you write 'afternoon', guests will expect a daytime feel, with lighter food and less formal dress. If you write 'evening', they may expect a later start and a more formal or party atmosphere. For a 5pm ceremony, many couples use 'late afternoon' or just state the time clearly without labelling it. That avoids confusion.
Also consider what happens after the ceremony. If you are serving a sit-down dinner at 6.30pm, that feels like an evening wedding. If you are having tea and cake at 5.30pm, that feels like an afternoon wedding. Match the wording to the actual schedule, not the clock. Guests will understand better if you write 'ceremony at 5pm, dinner to follow' than if you label it incorrectly.
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