A set of modified HSQC experiments designed for the study of 13C-enriched small molecules is introduced. It includes an improved sensitivity-enhanced HSQC experiment eliminating signal artifacts because of high-order 13C magnetization terms generated at high 13C enrichment. A broadband homonuclear 13C decoupling sequence based on Zangger and Sterk's method simplifies the complex 13C–13C multiplet structure in the F1 dimension of HSQC. When recording spectra at high resolution, the combination with a multiple-site modulation of the selective pulse outperforms the constant-time HSQC in terms of sensitivity and reliability. Finally, two pulse sequences reintroducing selected JCC couplings with selective pulses facilitate their assignments and measurements either in the splitting of the resulting doublets or by modulation of the signal amplitude. A sample of uniformly 92% 13C-enriched cholesterol is used as an example.