Their highly functional nature has endowed metal-organic frameworks (MOFs) with diverse applications. On this basis, a higher demand has been proposed for the preparation of novel-structured MOFs. Hollow MOFs have been intensively studied and exhibited versatile properties, and among the various methods, secondary-component incorporation has been proved promising in the design and preparation of complex structures with requisite properties. Herein, the synthesis and applications of secondary component incorporated MOFs and their derivatives are systematically reviewed. Two main methodologies, preincorporation and postmodification, are discussed in detail, and the role of the secondary component is demonstrated. Based on these introductions, the applications of those materials, including chemical catalysis, electrocatalysis, and energy storage applications, are summarized. Finally, a personal outlook for the future opportunities and challenges in this field is given.