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Psychologists believe that a student’s motiva-tion is influenced by a number of values/beliefs, interestsand attitudes that can be positive or negative in theireffects. Highly positively motivated students would believethat the task is of value (value beliefs), also with highexpectations that they would achieve success (expectancyand self-efficacy beliefs). This article analyzed the affec-tive factors in particular on the values and expectations ofMalaysian and Singaporean eighth-graders who partici-pated in the Trends in International Mathematics and Sci-ence Study (TIMSS) in the 2007 in relation to their scienceand mathematics achievement. The study explored if thesestudents’ values and expectation towards science andmathematics have any correlation with their achievementin science and mathematics. The data were obtained from4,466 Malaysian and 4,599 Singaporean Grade 8 studentsduring TIMSS 2007. Statistical Packages for the SocialSciences version 17 was used as plug-in along with IEAInternational Database analyzer Version 2.0 in data ana-lysis. A comprehensive investigation of the relationshipbetween the variables studied provides a clearer picture tothe role played by the variables in affecting students’achievement in science and mathematics. Educationalimplications were also deliberated by comparing these twocountries that have quite a number of similarities and dif-ferences as analyzed from the socio-cultural backgrounds,geographical structures and educational system.