We’re so used to seeing musicians do the late-night promo rounds that it almost gets robotic. Host interviews band, band plays song, host comes out to shake hands with band and say the name of the album. It’s rare for the musician to have any kind of human moment in the midst of all that. But Chan Marshall only has human moments. If you ever saw Cat Power early in Marshall’s career, you know that she has often had to push herself hard just to get through a performance. She’s worked hard to handle her anxiety, and she’s now a dependably great live performer. But there’s something enormously endearing about the way she took a quick breath to steady herself on Colbert last night, just before singing.

Tomorrow, Marshall will release Wanderer, the first new Cat Power album in six years. She was the musical guest on last night’s episode of Colbert’s Late Show, and on the show, she sang “Woman,” the album’s bluesy and vaguely feminist single. (Lana Del Rey sings on the album version, but she wasn’t there for the Colbert performance.) She sounded incredible, of course; she’s got one of the all-time great voices. And her band is sharp and steady, perfectly capable of conjuring the album’s expansive atmosphere.

But the real thrill in seeing Cat Power on late night is just seeing Cat Power on late night. Marshall is a vulnerable raw-nerve performer, and she tends to gain confidence as her performances go on. So to see her turn it on like that, and to put in the effort that it took, is a cool thing. Watch the performance below.

Wanderer is out 10/5 on Domino. Read our Cover Story on Cat Power here.