The fifth-seeded Matosevic of the United States fell to the Czech Republic's Jiri Vesely 6-3, 6-2 at the Racquet Club of Memphis.
Meanwhile, No. 7 seed Przysiezny of Poland was bounced by American Michael Russell 3-6, 6-3, 6-1.
Also Monday, U.S. player Tim Smyczek rallied for a 6-7 (5-7), 6-4, 6-3 decision over Australian Nick Kyrgios.
2014: The Year in Music [PHOTOS]