Evans triumphed 6-3 7-5 7-5 against world no65 Lukas Lacko to give Great Britain a surprise 1-0 lead, but Martin Klizan defeated Ward 6-2 4-6 6-4 7-6 to level the tie.
Going into the opening singles rubber it was expected that the biggest contest at the Braehead Arena would be a singing one between groups of boisterous students from the universities of Glasgow and Stirling.
However, world no276 Evans not only competed with his higher ranked opponent, but swept him aside in straight sets.
The 21-year-old began strongly, comfortably holding in his opening service game, before breaking at the first opportunity for a 2-0 lead.
He saved two break points in the fifth game, and after some brilliant defending managed to hang on and take the set 6-3 with a delicate drop volley.
With over 200 ranking places separating the players you would have expected a greater reaction from the Slovakian, who has been in great form in 2012 after reaching the third round of the Australian Open and his first career ATP final in Zagreb last week.
But Lacko struggled to grab hold of the match in the second set as breaks were traded back and forth, before Evans finally made the crucial breakthrough and served out for a two sets to love lead, taking the second 7-5.
Home fans began to shift uneasily in their seats as Evans’ level dropped in the middle of the third set, but the Birmingham-born ace regained his composure and persevered, eventually breaking Lacko for a 6-5 lead and serving out for a sensational victory.
“It’s definitely the best win of my career. There were some nerves at the start when I walked out, but I started pretty well and got on top,” said Evans.
Ward was unable to build on Evans’ opening marker as he fell in four sets to left-hander Martin Klizan in the day’s second singles rubber.
With talisman Andy Murray missing, the tie was always going to be a difficult one for Great Britain, but there were enough signs on day one to suggest that they can still progress.
Colin Fleming and Ross Hutchins take on Filip Polasek and Michal Mertinak on Saturday at 1pm in the pivotal doubles rubber.
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BIOGRAPHY: Ethan Hazard
BIOGRAPHY: Daniel Sturridge