[html] Is it possible to style a mouseover on an image map using CSS?

You could use Canvas

in HTML, simply add a canva

<canvas id="locations" width="400" height="300" style="border:1px solid #d3d3d3;">
Your browser can't read canvas</canvas>

And in Javascript (only an example, that will draw a rectangle on the picture)

var c = document.getElementById("locations");
var ctx = c.getContext("2d");
var img = new Image(); 
img.src = '{main_photo}';
img.onload = function() {    // after the pic is loaded
    ctx.drawImage(this,0,0); // add the picture
    ctx.beginPath();         // start the rectangle
    ctx.moveTo(50,50);
    ctx.lineTo(200,50);
    ctx.lineTo(200,200);
    ctx.lineTo(50,200);
    ctx.lineTo(50,50);

    ctx.strokeStyle = "sienna"; // set color
    ctx.stroke();               // apply color
    ctx.lineWidth = 5;
    // ctx.closePath();
};