Chapter represents when they first had sex.
Official:
Zhu Zhuqing (Fiancée) (Chapter 70)
Ning Rongrong (Fiancée) (Chapter 276 & 343)
Qian Renxue (Fiancée) (Chapter 567)
Unofficial:
Xiao Wu (Chapter 93)
Shui Yue'er (Chapter 143)
Zi Ji (Chapter 231)
Dugu Yan (Chapter 296)
Liu Erlong (Chapter 318)
Xue Wu (Chapter 372)
Shui Bing'er (Chapter 382)
Ah Yin (Chapter 407)
Bai Chenxiang (Chapter 440)
Yu Lingling (Maid) (Chapter 495)
Huo Wu (Chapter 564)
Meng Yi (Chapter 564)
Bibi Dong (Chapter 679)
Hu Liena (Chapter 693)
Sheng Ming (Goddess of life) (Chapter 721)
Xue Ke (Chapter 746)
Xiao Bai (Chapter 775)
Gu Yuena (Chapter 878)
Love Interest:
Wang Qui'er (Three Eyed Golden Lion)
Zhu Zhuyun
Bi Ji
Tang Yuehua
A Rou (Xiao Wu's mother)
Zi Zhenzhu (Disciple)
Bo Saixi
Bai Xiuxiu
Lan Nu'er (Demon Empress)
Lan Fuzi
Lorelei (Sea Woman Douluo)
Goddess of Kindness