The Briton, 24, chased home Ethiopia's Genzebe Dibaba, who took gold when Muir won bronze over 3,000m on Thursday.
The last time the 25-year-old competed in a pentathlon, at the 2015 European Indoor Championships in Prague, she finished just 13 points short of Nataliya Dobrynska's world record tally of 5013.
However, hitting the 2000m mark, Dibaba charged up as the pack started breaking up with Obiri moving to second.
With five laps remaining, the serious racing began.
With the pace slow initially, Dibaba injected life into the race with 1,000 metres to go and after a brief moment where Muir looked leggy, she quickened to move from sixth to third during a 200-metre stretch, thrusting her into the medal positions with 400 metres to go.
She has always been earmarked as the leading home hope in the post-Mo Farah years, and that was supported with European indoor golds at 1500m and 3000m last year.
Muir, who finished in four minutes 06.23 seconds, overtook Sifan Hassan on the final lap after the Holland runner finished ahead of her in the 3,000m.
The evening's first medal events were lacklustre high jump competitions as the men's and women's finals were held simultaneously for the first time and there were plenty of failures early on, with Great Britain's hope, Robbie Grabarz, failing with his three attempts at 2.25m. This is a great competition and the race was fantastic. "This time yesterday I was in a taxi halfway down the M6 and it was insane", Muir said.
Hassan moved off the rail and nearly into lane three in an expedient bid to hold off Muir. He became the first Hungarian to individually medal in a World Championship track event.
Muir will be out to stop her but the 27-year-old has proved nearly unstoppable indoors.
She was forced to get a £1500 taxi from Scotland to Birmingham on Wednesday after her flights were cancelled due to the snow. "I just thought "stay with them, be controlled" and I came off with silver this time". "We couldn't see the bonnet, the..."
Unbeaten over 5000m outdoors in 2017, Obiri finished fourth in 8:49.66, one place ahead of reigning U.S. indoor 1500m and 3000m champion Shelby Houlihan, who ran a strong last lap to finish fifth in 8:50.38, overhauling Ethiopia's Fantu Worku (8:50.54) and Klosterhalfen (8:51.79) in the final 200m.
"I knew even if I got ahead I could carry on my running smoothly", Doyle told BBC Sport. I just tried to take my time and not panic.
"Honestly I didn't expect to win this event", said Lysenko.
World 5000m Outdoors champion Hellen Obiri will take on defending champion Genzebe Dibaba of Ethiopia in the women's 3000m final as IAAF World Indoor Championships begin today from 8:15pm in Birmingham, United Kingdom.
The decoration of the two athletes required little more than an hour, but it all added up to quite a night for British Athletics, which arrived at the world titles with few dominant athletes but still rose to third in the overall medal table.