There are obvious reasons why precise internuclear distance measurements are essential in structural chemistry. Here we wish to give a practice-oriented review on the topic of accurate proton–proton distance measurements by solution NMR. The history of NOE and ROE methods is quite long, and the ambition has always been to tackle with the distance problem in a quantitative sense. The reader can find a basic introduction to relaxation and incoherent magnetization transfer by cross-relaxation. With the improvement of NMR instrument technology and improved measuring pulse sequences it has become everyday practice to run NOE/ROE experiments. Though the principles of quantitative NOE experiments have been known for decades, the full potential of the methods is rarely used for either small or big molecules. Here we suggest those improved experimental methods and their evaluation protocols that can be followed for accurate distance determination. Improvements in NOESY and ROESY sequences are presented, as well as the possibility of the “exact NOE” option for biopolymers. Hopefully, the interested reader can apply the techniques explained in this review.