There are several ways to define the word ‘beguiling’ (charm/amuse/cheat) – but I always think of the term ‘jolie-laide’ when I think of ‘beguiling’ – that sense of never quiiite being able to pin down what it is that interests/captivates/delights you…
I know a man. At first glance he is nothing special to look at. He’s not ugly…but he’s not beautiful. He’s …average, tending towards…. ‘eh. okay’ Nostrils you could drive a semi through. No chin to speak of. In need of a good exfoliator. so… eh. Except. Juuust when you have consigned him to the ‘eh’ heap, he turns his head, looks at you…
… and for a second you forget your own name.
That, to me, is beguiling. As far as actual beauty: resolutely pretty men, made beguiling by some bit of damage (Jason Momoa, with that cut bisecting his eyebrow; Pierce Brosnan with the scar above his mouth) those ‘flaws’ give them an air of (almost) gravitas, that humanizes their absurd beauty and makes me want to get to know what they might be like as a person; pretty, to me, is… pretty. And Floyd knows I love to look at pretty. But not for long because pretty quickly becomes boring, like nakedness (ymmv on that but I like to anticipate a body rather than having it delivered to me on a platter, like a side of beef. Post-beef, a sheet wound around the bits and pieces reignites my interest far more than the beef splayed out on the platter).
How does this relate to perfume? Well… I was looking through my Winter perfumes and came upon a decant of Aromatics Elixir…which, as you may know, is one of my most migraine-inducing perfumes! So. Why do I keep a decant of it? Because it is one of those perfumes that stays in my mind’s eye forever and it’s because there’s That Moment, when it turns its head and suddenly… and because it’s that beguiling I never can’t call up the scent. 
Mitsouko, for all its beauty, can also be beguiling in that same way – facets are, in turn, gorgeous and terrifying. And sometimes downright ugly. But always captivating.
Speaking of ‘jolie’, Jolie Madame is another ‘beguiler’ – I have never been able to wear it and I actually don’t think it’s at all pretty! But just the name brings forth the scent and it makes its presence known in ways that a prettier (to me) and more wearable scent could never do.
Do you have any beguiling scents? Beguiling men/women? What is it about those people & perfumes that captivates us so?

Here’s a vintage picture of one of the most beguiling women ever – definitely not ‘pretty’ ( imo). But completely captivating. A friend met her at Cannes a few years back and said it was one of the more confusing experiences he’d ever had – he was in the midst of some of the most gorgeous, glamourous women… and here ‘she’ is, with a nose like an eggplant (his actual description) and sallow skin… not in especially great shape. Yet he couldn’t take his eyes off her. Only a cool head prevented him from following her around like a puppy! He’s still trying to figure it out.

I think I kind of am attracted to those Jolie Laid sort of scents just like I’m attracted to people like that. I could appreciate Robert Redford or Brad Pitt, but when I was young I was kvelling over Willem DaFoe and James Remar.