Homeotropic alignment of liquid crystals (LCs) is one of the key modes used in commercial liquid crystal displays (LCDs) due to its advantages, such as high contrast ratios and fast response speed. Here, we report stable homeotropic LC alignment with a small pretilt angle in a nematic, negative LC host doped with additives including self-aligning agents, photoresponsive azo dyes, and reactive mesogen via an in situ self-assembled, dual-wavelength photoalignment approach. The underlying mechanism of stable, pretilted homeotropic LC alignment was further analyzed in detail. The achieved pretilted homeotropic LC cells are very stable against heat and UV light exposure and demonstrate excellent electro-optical characteristics. The experimental results show that such a noncontact, simple homeotropic alignment technique has big potential in many applications, such as high-quality LCDs, spatial light modulators, and other optoelectronic devices.