Expatriation is still a challenging task, although the determinants of expatriate adjustment and performance have been evaluated extensively. This study aimed to empirically investigate the influence of the expatriates’ personality and cross-cultural competence on social capital, cross-cultural adjustment, and performance with expatriates from foreign-owned multination firms in Taiwan. This study integrated three perspectives to explain expatriate success and failure. The first perspective involves expatriate-related factors, including the Big Five personality traits, and the emotional intelligence (otherwise known as emotional quotient or EQ) of expatriates. The second perspective is cross-cultural competence factors, including cultural intelligence, cultural adaptability, and cultural empathy. The third perspective is the social capital of expatriates, which includes leader-member exchange (LMX), perceived organizational support (POS). Furthermore, this study incorporated these perspectives into antecedents and identified their individual and combined effects on expatriates’ cross-cultural adjustment and performance. The findings of this study may be helpful for human resource managers in managing their expatriates. The findings may also help academicians in exploring expatriate management.