Devydenko, seeded 2nd, won the first set and recovered from a break in the second before his sprint finish in 78 minutes.
The 164th-ranked Henrych had not played an ATP match since last summer in Washington and made his third straight first-round exit at Rotterdam.
Spain's David Ferrer ended a run of Spanish suffering with a win over Simone Bolelli 6-4, 7-5.
Ferrer was untroubled in his straight-forward opener after reaching quarter-finals in Auckland and Melbourne so far this season as he handed number 66 Bolelli his sixth loss without a win against a top 10 player.
The victory was the lone bright spot for Spain after defeats for Tommy Robredo and Feliciano Lopez. Nicolas Mahut stopped Robredo 7-5, 6-4 while Gilles Simon accounted for Lopez 6-3, 6-4.
Rafael Nadal is flying Spanish colours as top seed, opening on Wednesday against Dmitry Tursunov of Russia.
Marcos Baghdatis made a brief initial visit to the event, losing his opening match 6-3, 3-6, 6-4 to resurgent Swede Robin Soderling.
Baghdatis had a short and sweet introduction to Rotterdam after falling foul of organisers with late injury pullouts over the past two editions.
But the Cypriot ranked 21st was all smiles after perhaps failing to perform as hoped with his wild card entry.
"I only arrived on Sunday night and had a tough time getting used to the court," he said after going out in an hour and three-quarters.
"The court was slow and the balls were heavy," he added. "That's a tough combination."
Baghdatis said that once he let the first set slip away against Soderling, ranked 44th and playing in only his second event after missing three months in late 2007 with a wrist injury, his chances were slim.
"I didn't feel good on the court, you can't give away a set to a guy serving so well. I knew I couldn't give him any more chances."
Soderling broke in the final game to close out victory, but came up short in the ace count 10 to 13.
Baghdatis hopes he is still on track for a return to the top 10, where he landed after making a surprise Australian Open finals appearance two years ago against Swiss ace Roger Federer.
"I got to the top 10, but I couldn't stay there. I was young and immature then, but I'm working on more consistency."
By Bill Scott, dpa