It’s very simple. you need to do something like below.
1: const string webUrl = "http://sp13:8080/sites/hr/";
2: const string sourceUrl = @"C:\Copy\emp.doc";
3: string[] destinationUrl = { @"http://sp13:8080/sites/hr/Documents/emp.doc";
   4: CopyService.CopyResult[] resultArray;
5: byte[] fileContents;
   6:  
7: var copyService = new CopyService.Copy
   8:   {
9: Url = webUrl + "/_vti_bin/copy.asmx",
  10:     Credentials = System.Net.CredentialCache.DefaultCredentials
  11:   };
  12:  
  13:  
14: var filedInfo = new CopyService.FieldInformation
  15:   {
16: DisplayName = "Title",
  17:     Type = CopyService.FieldType.Text,
18: Value = "Test"
  19:   };
  20:  
21: //add values to fields in the library using fieldInfoArray array
  22: CopyService.FieldInformation[] filedInfoArray = { filedInfo };
  23:  
24: //upload file using a file stream
25: using (var stream = new FileStream(sourceUrl, FileMode.Open, FileAccess.Read))
  26:  {
27: fileContents = new Byte[stream.Length];
  28:    var read = stream.Read(fileContents, 0, Convert.ToInt32(stream.Length));
  29:    stream.Close();
  30:   }
  31:  
32: var copyResult = copyService.CopyIntoItems(sourceUrl, destinationUrl, filedInfoArray, fileContents, out resultArray);
