High-entropy alloys (HEAs) are considered alternatives to traditional structural materials because of their superior mechanical, physical, and chemical properties. However, alloy composition combinations are too numerous to explore. Finding a rapid synthesis method to accelerate the development of HEA bulks is imperative. Existing in situ synthesis methods based on additive manufacturing are insufficient for efficiently controlling the uniformity and accuracy of components. In this work, laser powder bed fusion (L-PBF) is adopted for the in situ synthesis of equiatomic CoCrFeMnNi HEA from elemental powder mixtures. High composition accuracy is achieved in parallel with ensuring internal density. The L-PBF-based process parameters are optimized; and two different methods, namely, a multi-melting process and homogenization heat treatment, are adopted to address the problem of incompletely melted Cr particles in the single-melted samples. X-ray diffraction indicates that HEA microstructure can be obtained from elemental powders via L-PBF. In the triple-melted samples, a strong crystallographic texture can be observed through electron backscatter diffraction, with a maximum polar density of 9.92 and a high ultimate tensile strength (UTS) of (735.3 ± 14.1) MPa. The homogenization heat-treated samples appear more like coarse equiaxed grains, with a UTS of (650.8 ± 16.1) MPa and an elongation of (40.2% ± 1.3%). Cellular substructures are also observed in the triple-melted samples, but not in the homogenization heat-treated samples. The differences in mechanical properties primarily originate from the changes in strengthening mechanism. The even and flat fractographic morphologies of the homogenization heat-treated samples represent a more uniform internal microstructure that is different from the complex morphologies of the triple-melted samples. Relative to the multi-melted samples, the homogenization heat-treated samples exhibit better processability, with a smaller composition deviation, i.e., ≤ 0.32 at.%. The two methods presented in this study are expected to have considerable potential for developing HEAs with high composition accuracy and composition flexibility.