I'm trying to do something like this:

I think it could be done using background image and another image (mask) above it with a transparent center. But is it possible to do the same with pure css?
Whilst you can't apply a box-shadow directly to an image you could apply it with a :before or :after
    .shadow
    {
        display:block;
        position:relative;
    }
    
    img {
        width: 100%;
        height: 100%;
    }
    
    .shadow:before
    {
        display:block;
        content:'';
        position:absolute;
        width:100%;
        height:100%;
        -moz-box-shadow:inset 0px 0px 3px 1px rgba(0,0,0,1);
        -webkit-box-shadow:inset 0px 0px 3px 1px rgba(0,0,0,1);
        box-shadow:inset 0px 0px 3px 1px rgba(0,0,0,1);
    }
        <div class="shadow">
                <img src="http://lorempixel.com/400/200/" />
        </div>
Yess it's possible like this:
.img {
border:1px solid black;
}
.img:hover {
border: none;
box-shadow: 0 0 10px black inset;
}
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